JP5745662B2 - Two-stage hydrogen separation reformer - Google Patents

Two-stage hydrogen separation reformer Download PDF

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JP5745662B2
JP5745662B2 JP2014045870A JP2014045870A JP5745662B2 JP 5745662 B2 JP5745662 B2 JP 5745662B2 JP 2014045870 A JP2014045870 A JP 2014045870A JP 2014045870 A JP2014045870 A JP 2014045870A JP 5745662 B2 JP5745662 B2 JP 5745662B2
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hydrogen separation
separation membrane
hydrogen
alloy
gas
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JP2014133696A (en
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英人 黒川
英人 黒川
匠 西井
匠 西井
義則 白崎
義則 白崎
安田　勇
勇 安田
森永　正彦
正彦 森永
湯川　宏
宏 湯川
智憲 南部
智憲 南部
佳久 松本
佳久 松本
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Nagoya University NUC
Tokyo Gas Co Ltd
Institute of National Colleges of Technologies Japan
Tokai National Higher Education and Research System NUC
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Nagoya University NUC
Tokyo Gas Co Ltd
Institute of National Colleges of Technologies Japan
Tokai National Higher Education and Research System NUC
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Description

本発明は、２段式水素分離型改質器に関し、より具体的には、Ｐｄ系合金水素分離膜と周期律表５Ａ族金属合金水素分離膜を使用してなる２段式水素分離型改質器に関する。   The present invention relates to a two-stage hydrogen separation reformer, and more specifically, a two-stage hydrogen separation reformer using a Pd alloy hydrogen separation membrane and a periodic table 5A group metal alloy hydrogen separation membrane. It relates to the genitalia.

従来型の水素分離型改質器の水素分離膜には一般的にＰｄ系合金水素分離膜が使用されている。水素分離型改質器において、投入原料ガスつまり水素含有被処理ガス（炭化水素の水蒸気改質等により得られる水素を含む被処理ガス）に対して多くの水素分離膜を搭載すれば、分離される水素量も増えて効率的に水素製造が行えるが、Ｐｄ系合金水素分離膜は高価であるとともに、装置が大きくなる。   A Pd alloy hydrogen separation membrane is generally used as a hydrogen separation membrane of a conventional hydrogen separation reformer. In a hydrogen separation reformer, if a large number of hydrogen separation membranes are mounted on the input raw material gas, that is, the hydrogen-containing treated gas (treated gas containing hydrogen obtained by steam reforming of hydrocarbons, etc.), the hydrogen separation type reformer is separated. Although the amount of hydrogen to be produced can be increased and hydrogen can be produced efficiently, the Pd-based alloy hydrogen separation membrane is expensive and the apparatus becomes large.

Ｐｄ系合金からなる水素分離膜によって水素を選択的に透過精製し、効率的な水素製造を行うためには、例えば１次圧（反応側）＝０．８ＭＰａＧ、２次圧（透過側）＝−０．０６〜０ＭＰａＧ、５００〜５５０℃、Ｓ／Ｃ＝２．５〜３．５の条件において、原料投入量２〜６ｃｃ／ｍｉｎ／ｃｍ2、好ましくは３〜４ｃｃ／ｍｉｎ／ｃｍ2程度で運転するのが適当である。 To selectively permeate and purify hydrogen through a hydrogen separation membrane made of a Pd-based alloy and perform efficient hydrogen production, for example, primary pressure (reaction side) = 0.8 MPaG, secondary pressure (permeation side) = -0.06 to 0 MPaG, 500 to 550 ° C., S / C = 2.5 to 3.5, raw material input amount is 2 to 6 cc / min / cm 2 , preferably about 3 to 4 cc / min / cm 2 It is suitable to drive at.

Ｐｄ系合金水素分離膜のみの水素分離型改質器においては、そのように最適化された運転条件において、水素分離膜の面積を増やしたり、水素分離膜モジュールの搭載量を増やしたりしても、水素分離膜の増加分に値する水素製造量は得られない。   In a hydrogen separation reformer using only a Pd-based alloy hydrogen separation membrane, even if the area of the hydrogen separation membrane is increased or the mounting amount of the hydrogen separation membrane module is increased under such optimized operating conditions. Thus, the amount of hydrogen production that is equivalent to the increase in the hydrogen separation membrane cannot be obtained.

例えば、炭化水素の改質時における見掛けの水素透過係数が０．７×１０-8ｍｏｌ・ｍ-1・ｓ-1・Ｐａ-1/2である、長さ４５０ｍｍ、幅１２０ｍｍ、厚さ２０μｍのＰｄ系合金水素分離膜に、９５ＮＬ／ｈ（およそ３ｃｃ／ｍｉｎ／ｃｍ2）の１３Ａ都市ガスと、Ｓ／Ｃ（水蒸気／カーボン比）＝３の水蒸気を、１次側（反応側）を０．８ＭＰａＧで投入し、２次圧（透過側）を−０．０６ＭＰａＧにして、５５０℃において水素製造を行った場合を考えると、長さ６００ｃｍとして膜面積を３３．３％増加させた場合、水素製造量は２９４ＮＬ／ｈから３５５ＮＬ／ｈへと２０．７％しか増加しない。 For example, the apparent hydrogen permeation coefficient during hydrocarbon reforming is 0.7 × 10 −8 mol · m −1 · s −1 · Pa −1/2 , length 450 mm, width 120 mm, thickness 20 μm A Pd-based alloy hydrogen separation membrane of 95 NL / h (approximately 3 cc / min / cm 2 ) of 13 A city gas and S / C (water vapor / carbon ratio) = 3 of water vapor on the primary side (reaction side) Considering the case where hydrogen was produced at 550 ° C. with a secondary pressure (permeation side) of −0.06 MPaG and the membrane area was increased by 33.3% by 0.8 MPaG. Hydrogen production increases only 20.7% from 294 NL / h to 355 NL / h.

ところで、Ｎｂ、Ｖ、Ｔａなど元素の周期律表５Ａ族金属または５Ａ族金属を含む合金はＰｄ−Ａｇ合金などのＰｄ系合金と比較して高い水素透過係数Φを有しているが、水素脆化が起こるために水素分離膜としての使用が困難である。そこで水素脆化を抑制するために、添加元素を加えて水素脆化を抑制する方法などが提案されている（特許文献１、２）。しかし、添加物質を何％加えると言った単純な制御によって、単に高い溶解度や水素透過係数を得るだけでは、耐水素脆性と工業的に重要な高い水素透過速度の両立は困難であり、添加物質、添加量に加えて適切な使用温度、使用圧力（一次側及び二次側）を選択することが必要である。   By the way, the periodic table of elements such as Nb, V, Ta, etc., Group 5A metals or alloys containing Group 5A metals have a high hydrogen permeability coefficient Φ compared to Pd-based alloys such as Pd—Ag alloys. Since embrittlement occurs, it is difficult to use as a hydrogen separation membrane. Therefore, in order to suppress hydrogen embrittlement, methods for suppressing hydrogen embrittlement by adding additional elements have been proposed (Patent Documents 1 and 2). However, it is difficult to achieve both hydrogen embrittlement resistance and industrially important high hydrogen permeation rate by simply obtaining high solubility and hydrogen permeation coefficient by simply controlling what percentage of additive material is added. In addition to the addition amount, it is necessary to select an appropriate use temperature and use pressure (primary side and secondary side).

本発明者らは、ＰＣＴ曲線（＝圧力組成温度曲線）を利用することで、他成分添加によって水素固溶量を抑制しつつ、高い水素濃度差を実現する最適条件を求める方法を先に開発、提案している（特許文献３、４）。この方法によると、脆性破壊を起さない条件を明らかにすることで、低水素分圧、低圧差での使用が可能になることを純Ｎｂ、Ｎｂ−Ｗ合金において示した。しかし、その最高使用圧力は、０．０５ＭＰａ（絶対圧）と言う大気圧以下であり、高水素分圧では使用できなかった。   The present inventors have first developed a method for obtaining an optimum condition for realizing a high hydrogen concentration difference while suppressing the amount of hydrogen solid solution by adding other components by using a PCT curve (= pressure composition temperature curve). (Patent Documents 3 and 4). According to this method, it was shown that pure Nb and Nb-W alloys can be used at low hydrogen partial pressure and low pressure difference by clarifying the conditions that do not cause brittle fracture. However, the maximum working pressure is below atmospheric pressure of 0.05 MPa (absolute pressure) and cannot be used at a high hydrogen partial pressure.

特開２００１−１７０４６０号公報JP 2001-170460 A 特開２００６−０００７２２号公報JP 2006-000722 A 特願２００８−０７２６０７号（２００８年３月１９日出願）Japanese Patent Application No. 2008-072607 (filed on Mar. 19, 2008) 特願２００８−０７２６０９号（２００８年３月１９日出願）Japanese Patent Application No. 2008-072609 (filed on Mar. 19, 2008)

本発明者らは、今回、大気圧以上の水素分圧でも使用可能な５Ａ族金属合金水素分離膜を新たに見出した。すなわち、例えば５００℃において、Ｖ−Ｗ系合金水素分離膜であれば０．３ＭＰａ（絶対圧）まで使用可能であり、Ｔａ−Ｗ系合金水素分離膜であれば０．１５ＭＰａ（絶対圧）まで使用可能である。そして、５００℃における見掛けの水素透過係数は最大でＰｄ−Ａｇ合金の５倍であることを明らかにした（図１〜４）。   The present inventors have newly found a 5A group metal alloy hydrogen separation membrane that can be used even at a hydrogen partial pressure of atmospheric pressure or higher. That is, for example, at 500 ° C., a VW alloy hydrogen separation membrane can be used up to 0.3 MPa (absolute pressure), and a Ta—W alloy hydrogen separation membrane can be used up to 0.15 MPa (absolute pressure). It can be used. Then, it was clarified that the apparent hydrogen permeation coefficient at 500 ° C. is 5 times as large as that of the Pd—Ag alloy (FIGS. 1 to 4).

本発明は、そのように、例えば５００℃において、０．３ＭＰａ（絶対圧）まで使用可能なＶ−Ｗ系合金水素分離膜、０．１５ＭＰａ（絶対圧）まで使用可能なＴａ−Ｗ系合金水素分離膜を利用し、それらをＰｄ系合金水素分離膜と併用することにより、すなわち、Ｐｄ系合金水素分離膜と５Ａ族金属合金水素分離膜を併用することにより、従来の改質器より高い水素回収率が得られる２段式水素分離型改質器を提供することを目的とするものである。 The present invention, so, for example, in 500 ° C., 0.3MP a (absolute pressure) or available on a V-W-based alloy hydrogen separation membrane, 0.15MP a (absolute pressure) or available in Ta- By using W-based alloy hydrogen separation membranes and using them together with Pd-based alloy hydrogen separation membranes, that is, using Pd-based alloy hydrogen separation membranes and Group 5A metal alloy hydrogen separation membranes together, It is an object of the present invention to provide a two-stage hydrogen separation reformer that can obtain a higher hydrogen recovery rate than the reactor.

本発明（１）は、水素分離膜を支持する役割を果たす円筒状の多孔質支持体もしくは多孔板からなる支持体の外周面に水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。本発明（１）は、参考発明である。
本発明（２）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす円筒状の改質触媒兼多孔質支持体の外周面に水素分離膜を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。本発明（２）は、参考発明である。
本発明（３）は、水素分離膜を支持する役割を果たす筺状の多孔質支持体の外周面に水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。本発明（３）は、参考発明である。
本発明（４）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす筺状の改質触媒兼支持体の外周面に水素分離膜を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。本発明（４）は、参考発明である。
本発明（１）〜（４）の２段式水素分離型改質器において、被処理ガスの下流側に用いる５Ａ族金属合金水素分離膜としては、Ｖ−Ｗ系合金水素分離膜、Ｔａ−Ｗ系合金水素分離膜などを用いることができる。 In the present invention (1), a hydrogen separation membrane is arranged on the outer peripheral surface of a cylindrical porous support or a porous plate supporting the hydrogen separation membrane, and reformed on the outer periphery of the hydrogen separation membrane. A hydrogen separation reformer comprising a catalyst layer, wherein the hydrogen separation membrane uses a Pd-based alloy hydrogen separation membrane on the upstream side of the gas to be treated, and a group 5A on the downstream side of the gas to be treated. A two-stage hydrogen separation reformer characterized by using a metal alloy hydrogen separation membrane. The present invention (1) is a reference invention.
The present invention (2) is a hydrogen separation type in which a hydrogen separation membrane is disposed on the outer peripheral surface of a cylindrical reforming catalyst / porous support that simultaneously serves as a reforming catalyst and supports a hydrogen separation membrane. In the reformer, the hydrogen separation membrane uses a Pd-based alloy hydrogen separation membrane on the upstream side of the gas to be treated, and uses a 5A group metal alloy hydrogen separation membrane on the downstream side of the gas to be treated. Is a two-stage hydrogen separation reformer characterized by The present invention (2) is a reference invention.
In the present invention (3), a hydrogen separation membrane is disposed on the outer peripheral surface of a bowl-shaped porous support that plays a role of supporting the hydrogen separation membrane, and a reforming catalyst layer is disposed on the outer periphery of the hydrogen separation membrane. In the hydrogen separation type reformer, the hydrogen separation membrane uses a Pd alloy hydrogen separation membrane on the upstream side of the gas to be treated, and uses a 5A group metal alloy hydrogen separation membrane on the downstream side of the gas to be treated. A two-stage hydrogen separation reformer characterized by comprising: The present invention (3) is a reference invention.
The present invention (4) is a hydrogen separation reforming in which a hydrogen separation membrane is disposed on the outer peripheral surface of a bowl-shaped reforming catalyst / support that simultaneously serves as a reforming catalyst and supports a hydrogen separation membrane. The hydrogen separation membrane is characterized in that a Pd-based alloy hydrogen separation membrane is used on the upstream side of the gas to be processed, and a group 5A metal alloy hydrogen separation membrane is used on the downstream side of the gas to be processed. Is a two-stage hydrogen separation reformer. The present invention (4) is a reference invention.
In the two-stage hydrogen separation reformer of the present invention (1) to (4), the 5A group metal alloy hydrogen separation membrane used on the downstream side of the gas to be treated includes a VW alloy hydrogen separation membrane, Ta— A W-based alloy hydrogen separation membrane can be used.

本発明（５）は、水素分離膜を支持する役割を果たす円筒状の多孔質支持体もしくは多孔板からなる支持体の外周面に前記水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。
本発明（５）は、本願請求項１に係る発明である。 The present invention (5) is disposed the hydrogen separation membrane to the outer peripheral surface of the support consisting serves cylindrical porous support or the porous plate for supporting the hydrogen separation membrane, reforming the periphery of the hydrogen separation membrane A hydrogen separation type reformer comprising a catalyst layer, wherein the hydrogen separation membrane uses a Pd-based alloy hydrogen separation membrane upstream of the gas to be treated, and is disposed downstream of the gas to be treated. absolute pressure is two-stage hydrogen separation reformer which characterized by using a V alloy or Ta alloy hydrogen separation membrane can be used without causing brittle fracture even on 0.10MP a than at.
The present invention (5) is an invention according to claim 1 of the present application.

本発明（６）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす円筒状の改質触媒兼多孔質支持体の外周面に前記水素分離膜を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。
本発明（６）は、本願請求項２に係る発明である。 The present invention (6) is a hydrogen separation formed by arranging the hydrogen separation membrane to the outer peripheral surface of a cylindrical reforming catalyst and porous support serves to support the role and the hydrogen separation membrane as the reforming catalyst at the same time a type reformer, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the downstream side of the gas to be treated in 0.10MP a than on the absolute pressure A two-stage hydrogen separation type reformer characterized by using a V alloy or Ta alloy hydrogen separation membrane that can be used without causing brittle fracture.
The present invention (6) is an invention according to claim 2 of the present application.

本発明（７）は、水素分離膜を支持する役割を果たす筺状の多孔質支持体もしくは多孔板からなる支持体の外周面に前記水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。
本発明（７）は、本願請求項３に係る発明である。 The present invention (7), placing the hydrogen separation membrane to the outer peripheral surface of the support made of porous support or the porous plate serves enclosure for supporting the hydrogen separation membrane, reforming the periphery of the hydrogen separation membrane A hydrogen separation type reformer comprising a catalyst layer, wherein the hydrogen separation membrane uses a Pd-based alloy hydrogen separation membrane upstream of the gas to be treated, and is disposed downstream of the gas to be treated. absolute pressure is two-stage hydrogen separation reformer which characterized by using a V alloy or Ta alloy hydrogen separation membrane can be used without causing brittle fracture even on 0.10MP a than at.
The present invention (7) is an invention according to claim 3 of the present application.

本発明（８）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす筺状の改質触媒兼支持体の外周面に前記水素分離膜を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器である。
本発明（８）は、本願請求項４に係る発明である。 The present invention (8) is a hydrogen separation type reformer comprising the hydrogen separation membrane disposed on the outer peripheral surface of a bowl-shaped reforming catalyst / support that simultaneously serves as a reforming catalyst and supports the hydrogen separation membrane. a quality unit, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the even brittle fracture on 0.10MP a than on the downstream side at an absolute pressure of the gas to be treated It is a two-stage hydrogen separation reformer characterized by using a V alloy or Ta alloy hydrogen separation membrane that can be used without causing any problems.
The present invention (8) is an invention according to claim 4 of the present application.

本発明によれば、以下（１）〜（４）の効果が得られる。
（１）天然ガスなどの原燃料から、従来の改質器より高い水素回収率が得られる水素分離型改質器が実現できる。
（２）Ｐｄ等の貴金属の使用量を低減することで水素分離膜の低コスト化につながる。従来と同じ水素製造量が必要であれば、後段に５Ａ族金属合金水素分離膜を付与して前段のＰｄ系合金水素分離膜の量を低減できる。
（３）２段式水素分離膜によって、５００℃でもＰｄ系合金水素分離膜のみ５５０℃のときと同等の水素製造量が得られる。
（４）高い回収率で水素を引き抜くため、改質器のオフガス中のＣＯ2濃度が上昇し、圧縮液化によるオフガスからの効率的なＣＯ2分離回収が可能になる。 According to the present invention, the following effects (1) to (4) can be obtained.
(1) A hydrogen separation type reformer that can obtain a higher hydrogen recovery rate than a conventional reformer from a raw fuel such as natural gas can be realized.
(2) By reducing the amount of noble metal used such as Pd, the cost of the hydrogen separation membrane can be reduced. If the same amount of hydrogen production as before is required, a group 5A metal alloy hydrogen separation membrane can be provided in the subsequent stage to reduce the amount of the Pd-based alloy hydrogen separation membrane in the previous stage.
(3) With the two-stage hydrogen separation membrane, a hydrogen production amount equivalent to that at 550 ° C. can be obtained only at the Pd-based alloy hydrogen separation membrane even at 500 ° C.
(4) Since hydrogen is extracted at a high recovery rate, the CO 2 concentration in the reformer off-gas increases, and efficient CO 2 separation and recovery from the off-gas by compression liquefaction becomes possible.

図１はＶ−Ｗ系合金膜について、温度４００℃、４５０℃、５００℃における、雰囲気の水素圧力Ｐと固溶水素量Ｃの関係をプロットした図である。FIG. 1 is a graph plotting the relationship between the hydrogen pressure P of the atmosphere and the amount of dissolved hydrogen C at temperatures of 400 ° C., 450 ° C., and 500 ° C. for the VW type alloy film. 図２はＰｄ−２６Ａｇ合金、Ｎｂ−５Ｗ合金、Ｖ−５Ｗ合金について、水素透過速度試験の試験条件、結果を示す図である。FIG. 2 is a diagram showing test conditions and results of a hydrogen permeation rate test for Pd-26Ag alloy, Nb-5W alloy, and V-5W alloy. 図３はＴａ−Ｗ系合金膜について、温度４００℃、４５０℃、５００℃における、雰囲気の水素圧力Ｐと固溶水素量Ｃの関係をプロットした図である。FIG. 3 is a graph plotting the relationship between the hydrogen pressure P of the atmosphere and the amount C of solute hydrogen at temperatures of 400 ° C., 450 ° C., and 500 ° C. for the Ta—W alloy film. 図４はＰｄ−２６Ａｇ合金、Ｔａ−５Ｗ合金について、水素透過速度試験の試験条件、結果を示す図である。FIG. 4 is a diagram showing test conditions and results of a hydrogen permeation rate test for a Pd-26Ag alloy and a Ta-5W alloy. 図５は本発明の構成態様例１を説明する図である。FIG. 5 is a diagram for explaining a configuration example 1 of the present invention. 図６は本発明の構成態様例１を説明する図である。FIG. 6 is a diagram for explaining a configuration example 1 of the present invention. 図７は本発明の構成態様例２を説明する図である。FIG. 7 is a diagram for explaining a configuration example 2 of the present invention. 図８は本発明の構成態様例３を説明する図である。FIG. 8 is a diagram for explaining a configuration example 3 of the present invention. 図９は本発明の構成態様例４を説明する図である。FIG. 9 is a diagram for explaining a configuration example 4 of the present invention.

本発明（１）は、水素分離膜を支持する役割を果たす円筒状の多孔質支持体もしくは多孔板からなる支持体の外周面に水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする。本発明（１）は、参考発明である。
本発明（２）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす円筒状の改質触媒兼多孔質支持体の外周面に水素分離膜を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする。本発明（２）は、参考発明である。
本発明（３）は、水素分離膜を支持する役割を果たす筺状の多孔質支持体の外周面に水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする。本発明（３）は、参考発明である。
本発明（４）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす筺状の改質触媒兼支持体の外周面に水素分離膜を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、被処理ガスの下流側には５Ａ族金属合金水素分離膜を用いてなることを特徴とする。本発明（４）は、参考発明である。
本発明（１）〜（４）の２段式水素分離型改質器において、被処理ガスの下流側に用いる５Ａ族金属合金水素分離膜としては、Ｖ−Ｗ系合金水素分離膜、Ｔａ−Ｗ系合金水素分離膜などを用いることができる。 In the present invention (1), a hydrogen separation membrane is arranged on the outer peripheral surface of a cylindrical porous support or a porous plate supporting the hydrogen separation membrane, and reformed on the outer periphery of the hydrogen separation membrane. It is a hydrogen separation type reformer formed by arranging a catalyst layer. The hydrogen separation membrane is characterized in that a Pd-based alloy hydrogen separation membrane is used on the upstream side of the gas to be processed, and a 5A group metal alloy hydrogen separation membrane is used on the downstream side of the gas to be processed. The present invention (1) is a reference invention.
The present invention (2) is a hydrogen separation type in which a hydrogen separation membrane is disposed on the outer peripheral surface of a cylindrical reforming catalyst / porous support that simultaneously serves as a reforming catalyst and supports a hydrogen separation membrane. It is a reformer. The hydrogen separation membrane is characterized in that a Pd-based alloy hydrogen separation membrane is used on the upstream side of the gas to be processed, and a 5A group metal alloy hydrogen separation membrane is used on the downstream side of the gas to be processed. The present invention (2) is a reference invention.
In the present invention (3), a hydrogen separation membrane is disposed on the outer peripheral surface of a bowl-shaped porous support that plays a role of supporting the hydrogen separation membrane, and a reforming catalyst layer is disposed on the outer periphery of the hydrogen separation membrane. This is a hydrogen separation type reformer. The hydrogen separation membrane is characterized in that a Pd-based alloy hydrogen separation membrane is used on the upstream side of the gas to be processed, and a 5A group metal alloy hydrogen separation membrane is used on the downstream side of the gas to be processed. The present invention (3) is a reference invention.
The present invention (4) is a hydrogen separation reforming in which a hydrogen separation membrane is disposed on the outer peripheral surface of a bowl-shaped reforming catalyst / support that simultaneously serves as a reforming catalyst and supports a hydrogen separation membrane. It is a vessel. The hydrogen separation membrane is characterized in that a Pd-based alloy hydrogen separation membrane is used on the upstream side of the gas to be processed, and a 5A group metal alloy hydrogen separation membrane is used on the downstream side of the gas to be processed. The present invention (4) is a reference invention.
In the two-stage hydrogen separation reformer of the present invention (1) to (4), the 5A group metal alloy hydrogen separation membrane used on the downstream side of the gas to be treated includes a VW alloy hydrogen separation membrane, Ta— A W-based alloy hydrogen separation membrane can be used.

本発明（５）は、水素分離膜を支持する役割を果たす円筒状の多孔質支持体もしくは多孔板からなる支持体の外周面に前記水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする。
本発明（５）は、本願請求項１に係る発明である。 The present invention (5) is disposed the hydrogen separation membrane to the outer peripheral surface of the support consisting serves cylindrical porous support or the porous plate for supporting the hydrogen separation membrane, reforming the periphery of the hydrogen separation membrane This is a hydrogen separation type reformer formed by arranging a porous catalyst layer. Then, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the downstream side of the gas to be treated without causing brittle fracture at an absolute pressure in 0.10MP a following Usage It is characterized by using a V alloy or Ta alloy hydrogen separation membrane.
The present invention (5) is an invention according to claim 1 of the present application.

本発明（６）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす円筒状の改質触媒兼多孔質支持体の外周面に前記水素分離膜を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする。
本発明（６）は、本願請求項２に係る発明である。 The present invention (6) is a hydrogen separation formed by arranging the hydrogen separation membrane to the outer peripheral surface of a cylindrical reforming catalyst and porous support serves to support the role and the hydrogen separation membrane as the reforming catalyst at the same time It is a mold reformer. Then, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the downstream side of the gas to be treated without causing brittle fracture at an absolute pressure in 0.10MP a following Usage It is characterized by using a V alloy or Ta alloy hydrogen separation membrane.
The present invention (6) is an invention according to claim 2 of the present application.

本発明（７）は、水素分離膜を支持する役割を果たす筺状の多孔質支持体もしくは多孔板からなる支持体の外周面に前記水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてな
ることを特徴とする。
本発明（７）は、本願請求項３に係る発明である。 The present invention (7), placing the hydrogen separation membrane to the outer peripheral surface of the support made of porous support or the porous plate serves enclosure for supporting the hydrogen separation membrane, reforming the periphery of the hydrogen separation membrane This is a hydrogen separation type reformer formed by arranging a porous catalyst layer. Then, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the downstream side of the gas to be treated without causing brittle fracture at an absolute pressure in 0.10MP a following Usage It is characterized by using a V alloy or Ta alloy hydrogen separation membrane.
The present invention (7) is an invention according to claim 3 of the present application.

本発明（８）は、改質触媒としての役割と水素分離膜を支持する役割を同時に果たす筺状の改質触媒兼支持体の外周面に前記水素分離膜を配置してなる水素分離型改質器である。そして、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする。
本発明（８）は、本願請求項４に係る発明である。 The present invention (8) is a hydrogen separation type reformer comprising the hydrogen separation membrane disposed on the outer peripheral surface of a bowl-shaped reforming catalyst / support that simultaneously serves as a reforming catalyst and supports the hydrogen separation membrane. It is a quality device. Then, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the downstream side of the gas to be treated without causing brittle fracture at an absolute pressure in 0.10MP a following Usage It is characterized by using a V alloy or Ta alloy hydrogen separation membrane.
The present invention (8) is an invention according to claim 4 of the present application.

例えば、Ｐｄ系合金水素分離膜を用いた水素分離では、シーベルトの法則（Ｓｉｅｖｅｒｔ’ｓ ｌａｗ：Ｃ＝ＫＰ1/2。以下“シーベルツ則”と略称する。）に従うため、高い水素透過量Ｊ（Ｊ＝Ｄ・ΔＣ／ｄ、Ｄは拡散係数、ΔＣは固溶水素量差、ｄは膜厚）を稼ぐためにある程度の水素分圧差（ΔＰ）が必要であるが、Ｎｂはシーベルツ則に従わない領域があることがわかった。このため、低水素濃度においても水素圧力差や水素分圧差が発生すれば、高い固溶水素量差（ΔＣ）が得られ、高い水素透過量（Ｊ）を得ることができる。 For example, in hydrogen separation using a Pd-based alloy hydrogen separation membrane, the Siebert's law (Sievert's law: C = KP 1/2, hereinafter abbreviated as “Siebert's law”) is used. (J = D · ΔC / d, where D is the diffusion coefficient, ΔC is the difference in the amount of dissolved hydrogen, and d is the film thickness), a certain hydrogen partial pressure difference (ΔP) is required. It turns out that there are areas that do not follow. For this reason, if a hydrogen pressure difference or a hydrogen partial pressure difference occurs even at a low hydrogen concentration, a high solid solution hydrogen amount difference (ΔC) can be obtained, and a high hydrogen permeation amount (J) can be obtained.

使用温度でのＰＣＴ曲線を測定することで、合金の使用可能な水素圧を決定できる。例えば、５００℃においてＶ−Ｗ系合金は０．３ＭＰａ（絶対圧）以下、Ｔａ−Ｗ系合金は０．１５ＭＰａ（絶対圧）以下の水素分圧であれば水素分離膜として使用可能である（図１、図３）。 By measuring the PCT curve at the operating temperature, the usable hydrogen pressure of the alloy can be determined. For example, used as a V-W-based alloy 0.3MP a (absolute pressure) hereinafter, Ta-W alloy is 0.15MP a (absolute pressure) of hydrogen if the hydrogen partial pressure below the separation membrane at 500 ° C. It is possible (FIGS. 1 and 3).

また、水素の透過流束Ｊと合金の膜厚ｄの積であるＪ・ｄ値の評価から圧力条件によっては、Ｖ−Ｗ系合金やＴａ−Ｗ系合金がＰｄ−Ａｇ合金と比較して高い水素透過速度を得ることが分かった（図２、図４）。   Also, depending on the pressure condition from the evaluation of the J · d value, which is the product of the hydrogen permeation flux J and the film thickness d of the alloy, the VW alloy and the Ta—W alloy may be compared with the Pd—Ag alloy. It was found that a high hydrogen permeation rate was obtained (FIGS. 2 and 4).

図２のとおり、５００℃において、水素透過条件、プロセス側（一次側）／透過側（二次側）＝０．２０ＭＰａ／０．０１ＭＰａの場合、見掛けの水素透過能Φは、Ｐｄ−２６Ａｇ合金が２．３×１０-8（ｍｏｌ-1・ｍ-1・ｓ-1・Ｐａ-1/2）であるのに対し、Ｖ−５Ｗ合金膜１．２×１０-7（ｍｏｌ-1・ｍ-1・ｓ-1・Ｐａ-1/2）と約５倍であり、同じ面積、同じ厚さの分離膜であれば、約５倍の水素透過量が得られる。 As shown in FIG. 2, at 500 ° C., when hydrogen permeation condition, process side (primary side) / permeation side (secondary side) = 0.20 MPa / 0.01 MPa, the apparent hydrogen permeation capacity Φ is Pd-26Ag alloy Is 2.3 × 10 −8 (mol −1 · m −1 · s −1 · Pa −1/2 ), whereas V-5W alloy film 1.2 × 10 −7 (mol −1 · m −1 · s −1 · Pa −1/2 ) and about 5 times as long as a separation membrane having the same area and thickness, a hydrogen permeation amount of about 5 times can be obtained.

上述のＰｄ系合金水素分離膜の終端部分におけるガス組成は、５５０℃において、ＣＨ4＝７．０％、Ｈ2Ｏ＝５１．６％、ＣＯ2＝２６．９％、Ｈ2＝１２．６％であり、出口部分における水素分圧は０．１１ＭＰａ（絶対圧）となるため、プロセスガス側の圧力が０．８ＭＰａＧであっても、Ｐｄ系合金水素分離膜の後段においてＶ−Ｗ系合金水素分離膜やＴａ−Ｗ系合金水素分離膜の使用が可能となる。 The gas composition in the terminal portion of the Pd-based alloy hydrogen separation membrane described above is CH 4 = 7.0%, H 2 O = 51.6%, CO 2 = 26.9%, H 2 = 12. 6%, and the hydrogen partial pressure at the outlet portion is 0.11 MPa (absolute pressure). Therefore, even if the pressure on the process gas side is 0.8 MPaG, the VW system is used in the subsequent stage of the Pd-based alloy hydrogen separation membrane. An alloy hydrogen separation membrane or a Ta-W alloy hydrogen separation membrane can be used.

Ｖ−Ｗ系合金膜やＴａ−Ｗ系合金膜を使用した水素分離膜を、Ｐｄ系合金水素分離膜の後段、改質器上部の温度が５００℃以下の位置に設置すれば、Ｐｄ系合金水素分離膜のプロセス側オフガスからさらに水素を分離し、高い水素製造量が得られる水素分離型改質器が実現できる。   If a hydrogen separation membrane using a V-W alloy membrane or a Ta-W alloy membrane is installed at a position after the Pd alloy hydrogen separation membrane and at a temperature above the reformer, the Pd alloy It is possible to realize a hydrogen separation reformer that further separates hydrogen from the process-side off-gas of the hydrogen separation membrane to obtain a high hydrogen production amount.

上述のＰｄ系合金水素分離膜の後段に長さ１５０ｍｍ（Ｐｄ系合金水素分離膜の３３．３％）、幅１２０ｍｍ、厚さ４０μｍ（加工性がＰｄ系合金より低いため）、見掛けの水素透過係数が３．５×１０-8ｍｏｌ-1・ｍ-1・ｓ-1・Ｐａ-1/2（Ｐｄ−Ａｇ合金の約５倍）の５Ａ族金属合金水素分離膜を５００℃の温度環境下に設置した場合、原料転化率はＰｄ系合金水素分離膜のみの場合の８０．４％から９１．１％へ増加し、水素製造量は３６７ＮＬ／ｈとＰｄ系合金水素分離膜のみを用いた場合の水素製造量２９４ＮＬ／ｈに対して２４．８％増加する。このように、Ｐｄ系合金水素分離膜の面積を増加させた場合と比較して、低コストで高効率な水素分離型改質器を実現できる。 After the above-mentioned Pd alloy hydrogen separation membrane, the length is 150 mm (33.3% of the Pd alloy hydrogen separation membrane), the width is 120 mm, and the thickness is 40 μm (because the workability is lower than that of the Pd alloy). 5A group metal alloy hydrogen separation membrane with a coefficient of 3.5 × 10 −8 mol −1 · m −1 · s −1 · Pa −1/2 (about 5 times that of Pd—Ag alloy) When installed below, the raw material conversion rate increases from 80.4% in the case of only the Pd alloy hydrogen separation membrane to 91.1%, and the hydrogen production amount is 367 NL / h and only the Pd alloy hydrogen separation membrane is used. Increase by 24.8% against the hydrogen production amount of 294 NL / h. Thus, compared with the case where the area of the Pd-based alloy hydrogen separation membrane is increased, a low-cost and high-efficiency hydrogen separation reformer can be realized.

また、Ｐｄ系合金水素分離膜を５５０℃で使用する場合は、Ｐｄ系合金水素分離膜の終端部分における水素分圧が０．１５ＭＰａ（絶対圧）以下になればＶ−Ｗ系合金水素分離膜やＴａ−Ｗ系合金水素分離膜が使用できるので、上述のＰｄ系合金水素分離膜の長さを４５０ｃｍから３００ｃｍへ短くして〔Ｐｄ系合金水素分離膜の終端部分における水素分圧が０．１４ＭＰａ（絶対圧）〕、後段に１５０ｃｍの５Ａ族金属合金水素分離膜を設置してもよい。   When the Pd-based alloy hydrogen separation membrane is used at 550 ° C., if the hydrogen partial pressure at the terminal portion of the Pd-based alloy hydrogen separation membrane is 0.15 MPa (absolute pressure) or less, the V-W type alloy hydrogen separation membrane is used. And the Ta—W alloy hydrogen separation membrane can be used, the length of the Pd alloy hydrogen separation membrane is reduced from 450 cm to 300 cm [the hydrogen partial pressure at the terminal portion of the Pd alloy hydrogen separation membrane is 0. 14 MPa (absolute pressure)] and a 150 cm 5A group metal alloy hydrogen separation membrane may be installed in the subsequent stage.

つまり、Ｐｄ系合金水素分離膜の一部を５Ａ族金属合金水素分離膜に置換することが可能である。このとき、原料転化率は８２．８％であり、水素製造量は２９４ＮＬ／ｈから３２５ＮＬ／ｈへと、Ｐｄ系合金水素分離膜のみの場合と比較して１０．３％増加する。５Ａ族金属合金水素分離膜の膜厚を２０μｍまで薄くすることが可能であれば、原料転化率は９３．９％となり、水素製造量は３８２ＮＬ／ｈへと２９．８％増加する。   That is, a part of the Pd-based alloy hydrogen separation membrane can be replaced with a 5A group metal alloy hydrogen separation membrane. At this time, the raw material conversion is 82.8%, and the hydrogen production amount is increased by 10.3% from 294 NL / h to 325 NL / h compared to the case of only the Pd-based alloy hydrogen separation membrane. If the thickness of the Group 5A metal alloy hydrogen separation membrane can be reduced to 20 μm, the raw material conversion will be 93.9%, and the hydrogen production will increase by 29.8% to 382 NL / h.

反応炉全体をほぼ均一な温度にすることが可能であって、５００℃で運転を行う場合は、反応管の入口部分のみにＰｄ系合金水素分離膜があれば十分に水素分圧を０．１５ＭＰａ（絶対圧）以下に下げられることができる。９５ＮＬ／ｈ（およそ３ｃｍ3／ｍｉｎ／ｃｍ2）の１３Ａ都市ガスと、Ｓ／Ｃ（水蒸気／カーボン比）＝３の水蒸気を、一次側（改質側）を０．８ＭＰａＧで投入し、二次側（透過側）を−０．０６ＭＰａＧにして、５００℃において水素製造を行った場合、Ｐｄ系合金水素分離膜の長さ９０ｃｍ（４５０ｃｍの２０％）の場合、Ｐｄ系合金水素分離膜終端部分における水素分圧＝０．１３ＭＰａ（絶対圧）であり、後段で５Ａ族金属合金水素分離膜が使用できる。 It is possible to bring the entire reaction furnace to a substantially uniform temperature. When the operation is performed at 500 ° C., the hydrogen partial pressure is sufficiently reduced to 0.degree. It can be lowered to 15 MPa (absolute pressure) or less. 95 NL / h (approximately 3 cm 3 / min / cm 2 ) of 13 A city gas, S / C (steam / carbon ratio) = 3 steam, and primary side (reformed side) at 0.8 MPaG were added. When hydrogen production is performed at 500 ° C. with a secondary side (permeation side) of −0.06 MPaG, when the length of the Pd alloy hydrogen separation membrane is 90 cm (20% of 450 cm), the end of the Pd alloy hydrogen separation membrane The hydrogen partial pressure in the portion is 0.13 MPa (absolute pressure), and a 5A metal alloy hydrogen separation membrane can be used in the subsequent stage.

５Ａ族金属合金水素分離膜の長さ３６０ｃｍ（４５０ｃｍの８０％）の場合、水素製造量は３０６ＮＬ／ｈであり、５５０℃、Ｐｄ系合金水素分離膜のみの場合の２９４ＮＬ／ｈと比較して４．０％増加する。これにより、Ｐｄ系合金水素透過の使用量を大幅に減らすことができ、原材料コストを低減できるだけでなく、反応炉の運転温度を低下させることで、反応管加熱のための投入エネルギーを低減し、放熱等のエネルギーロスを低く抑えることで高効率化が可能となる。   When the length of the group 5A metal alloy hydrogen separation membrane is 360 cm (80% of 450 cm), the amount of hydrogen produced is 306 NL / h, compared to 294 NL / h in the case of only 550 ° C. and Pd alloy hydrogen separation membrane. Increase by 4.0%. As a result, the amount of Pd-based alloy hydrogen permeation can be greatly reduced, not only reducing raw material costs, but also reducing the input energy for heating the reaction tube by lowering the operating temperature of the reactor, High efficiency can be achieved by keeping energy loss such as heat radiation low.

また、改質ガスつまり水素含有ガスから高い回収率で水素を引き抜くため、改質器のオフガス中のＣＯ2濃度が相対的に上昇する。現在、世界最高効率を実現している出願人の４０Ｎｍ3／ｈメンブレンリフォーマー（改良型）の１００％出力時＝４０Ｎｍ3／ｈ水素製造時の改質器オフガス中のＣＯ2濃度は７２．２％であるが、条件によってはこれより高いＣＯ2濃度を得ることが可能である。２段式水素分離型改質器のオフガスからは、圧縮液化のみによって、より高効率にＣＯ2を分離し回収することが可能である。 Further, since hydrogen is extracted from the reformed gas, that is, the hydrogen-containing gas, at a high recovery rate, the CO 2 concentration in the off-gas of the reformer relatively increases. At the time of 100% output of the applicant's 40 Nm 3 / h membrane reformer (improved type) that currently achieves the world's highest efficiency = 40 Nm 3 / h The CO 2 concentration in the reformer off-gas during hydrogen production is 72.2 %, But depending on the conditions, higher CO 2 concentrations can be obtained. From the off-gas of the two-stage hydrogen separation reformer, CO 2 can be separated and recovered with higher efficiency only by compression liquefaction.

〈本発明の構成態様例１〉
図５〜６は、本発明の構成態様例１を説明する図である。図５（ａ）は２種類の合金膜を設置した水素分離器１の斜視図、図５（ｂ）は２種類の合金水素分離膜を設置した水素分離器１を収容した容器３の断面図である。図５（ｂ）、図６（ａ）中、改質触媒層として示しているように、容器３とそれに収容された水素分離器１と間には改質触媒層が配置されている。 <Configuration Example 1 of the Present Invention>
5-6 is a figure explaining the structural example 1 of this invention. FIG. 5A is a perspective view of the hydrogen separator 1 provided with two types of alloy membranes, and FIG. 5B is a cross-sectional view of the container 3 containing the hydrogen separator 1 provided with two types of alloy hydrogen separation membranes. It is. As shown as the reforming catalyst layer in FIGS. 5B and 6A, the reforming catalyst layer is disposed between the container 3 and the hydrogen separator 1 accommodated therein.

図５（ａ）のとおり、水素分離器１は合金からなる筺体の左右両面にそれぞれ間隔を置いてＰｄ系合金水素分離膜と５Ａ族金属合金水素分離膜との２種類の合金水素分離膜を順次配置して構成される。２種類の合金水素分離膜の配置は、プロセスガス（原燃料＋水蒸気）の流れ方向でみて、まずＰｄ系合金水素分離膜を配置し、次いで５Ａ族金属合金水素分離膜を配置する。水素分離器１と筺状容器３との間には改質触媒層が配置される。符号４はプロセスガス導入管であり、その下端部で開口している。   As shown in FIG. 5 (a), the hydrogen separator 1 includes two types of alloy hydrogen separation membranes, a Pd alloy hydrogen separation membrane and a 5A group metal alloy hydrogen separation membrane, spaced apart from each other on the left and right sides of the alloy casing. Sequentially arranged. As for the arrangement of the two types of alloy hydrogen separation membranes, a Pd-based alloy hydrogen separation membrane is first arranged, and then a Group 5A metal alloy hydrogen separation membrane is arranged, as viewed in the flow direction of the process gas (raw fuel + water vapor). A reforming catalyst layer is disposed between the hydrogen separator 1 and the bowl-shaped vessel 3. Reference numeral 4 denotes a process gas introduction pipe, which is open at the lower end thereof.

原燃料と水蒸気の混合ガスであるプロセスガスは、その導入管４を介して導入される。容器３内の下端部に放出されたプロセスガスは、水素分離器１と容器３との間の間隙を上昇しながら改質されて水素を生成する。生成水素を含むプロセスガスは、水素分離器１と容器３との間の間隙を上昇しながら、まず、水素分離器１のうちＰｄ系合金水素分離膜を透過して精製され、さらに５Ａ族金属合金水素分離膜を透過して精製される。精製水素は、水素導出管５を介して取り出される。   A process gas, which is a mixed gas of raw fuel and water vapor, is introduced through the introduction pipe 4. The process gas released to the lower end portion in the container 3 is reformed while raising the gap between the hydrogen separator 1 and the container 3 to generate hydrogen. The process gas containing the generated hydrogen is first purified through a Pd-based alloy hydrogen separation membrane in the hydrogen separator 1 while raising the gap between the hydrogen separator 1 and the vessel 3, and further, a group 5A metal It is purified by permeating the alloy hydrogen separation membrane. Purified hydrogen is taken out through the hydrogen outlet pipe 5.

図６（ｂ）に、プロセスガス側水素分圧と水素分離器１（分離膜モジュール）の下端からの距離との関係を示している。５Ａ族金属合金水素分離膜は、プロセスガス側水素分圧が小さい領域で有効であることから、図６（ａ）中“５Ａ族金属合金水素分離膜”として示すように、水素分離器１（分離膜モジュール）の上端部、すなわち下端からの距離が大きい箇所に配置する。   FIG. 6B shows the relationship between the process gas side hydrogen partial pressure and the distance from the lower end of the hydrogen separator 1 (separation membrane module). Since the group 5A metal alloy hydrogen separation membrane is effective in a region where the process gas side hydrogen partial pressure is small, as shown as “group 5A metal alloy hydrogen separation membrane” in FIG. The separation membrane module is disposed at the upper end of the separation membrane module, that is, at a location where the distance from the lower end is large.

図６（ｂ）中“５Ａ族金属合金膜使用可能水素分圧上限”として示す点線より左側がプロセスガス側水素分圧が低い領域であり、その領域に“５Ａ族金属合金膜”を配置する（図６（ａ）中“５Ａ族金属合金膜”として示す箇所を含む領域）。この点は〈本発明の構成態様例２〉〜〈本発明の構成態様例４〉においても同様である。   In FIG. 6B, the left side of the dotted line shown as “Upper limit of hydrogen partial pressure that can be used for group 5A metal alloy film” is a region where the process gas side hydrogen partial pressure is low, and “group 5A metal alloy film” is arranged in that region. (A region including a portion shown as “Group 5A metal alloy film” in FIG. 6A). This point is the same as in <Structural aspect example 2> to <Structural aspect example 4 of the present invention>.

〈本発明の構成態様例２〉
図７は、本発明の構成態様例２を説明する図である。図７（ａ）は２個の各筺体に２種類の合金水素分離膜をそれぞれ配置した水素分離器１、２の斜視図、図７（ｂ）は２種類の合金水素分離膜を設置した水素分離器１を収容した筺状容器３の断面図である。図７（ｂ）中、改質触媒層として示しているように、筺状容器３とそれに収容された水素分離器１と間には改質触媒層が配置されている。改質触媒層は、図６（ａ）を利用して説明すると、下部から上部にわたり層状に配置される。 <Configuration Example 2 of the Present Invention>
FIG. 7 is a diagram for explaining a configuration aspect example 2 of the present invention. FIG. 7A is a perspective view of the hydrogen separators 1 and 2 in which two types of alloy hydrogen separation membranes are respectively arranged in two casings, and FIG. 7B is a hydrogen in which two types of alloy hydrogen separation membranes are installed. It is sectional drawing of the bowl-shaped container 3 which accommodated the separator 1. FIG. As shown as a reforming catalyst layer in FIG. 7B, a reforming catalyst layer is disposed between the bowl-shaped container 3 and the hydrogen separator 1 accommodated therein. When the reforming catalyst layer is described with reference to FIG. 6A, the reforming catalyst layer is arranged in layers from the lower part to the upper part.

図７（ａ）のとおり、水素分離器１は合金からなる下部の筺体の左右両面にＰｄ系合金水素分離膜を配置して構成され、水素分離器２は合金からなる上部の筺体の左右両面に５Ａ族金属合金水素分離膜を配置して構成される。水素分離器１では合金からなる筺体の左右両面にＰｄ系合金水素分離膜が配置され、水素分離器２では合金からなる筺体の左右両面に５Ａ族金属合金水素分離膜が配置されて構成される。   As shown in FIG. 7A, the hydrogen separator 1 is configured by arranging Pd-based alloy hydrogen separation membranes on both the left and right sides of the lower casing made of an alloy, and the hydrogen separator 2 is formed on both the left and right sides of the upper casing made of an alloy. And 5A group metal alloy hydrogen separation membrane. In the hydrogen separator 1, Pd-based alloy hydrogen separation membranes are arranged on both the left and right sides of the alloy casing, and in the hydrogen separator 2, a group 5A metal alloy hydrogen separation membrane is arranged on both the left and right sides of the alloy casing. .

水素分離器１と水素分離器２との配置は、プロセスガス（原燃料＋水蒸気）の流れ方向でみて、まずＰｄ系合金水素分離膜を配置された水素分離器１が配置され、次いで５Ａ族金属合金水素分離膜が配置された水素分離器２が配置される。水素分離器１と水素分離器２は連結管Ｋにより連結されている。水素分離器１、水素分離器２と筺状容器３との間には改質触媒層が配置される。符号４はプロセスガス導入管であり、その下端部で開口している。   The hydrogen separator 1 and the hydrogen separator 2 are arranged in the flow direction of the process gas (raw fuel + steam). First, the hydrogen separator 1 on which the Pd-based alloy hydrogen separation membrane is arranged is arranged, and then the group 5A A hydrogen separator 2 in which a metal alloy hydrogen separation membrane is disposed is disposed. The hydrogen separator 1 and the hydrogen separator 2 are connected by a connecting pipe K. A reforming catalyst layer is disposed between the hydrogen separator 1, the hydrogen separator 2, and the bowl-shaped container 3. Reference numeral 4 denotes a process gas introduction pipe, which is open at the lower end thereof.

原燃料と水蒸気の混合ガスであるプロセスガスは、その導入管４を介して導入される。容器３内の下端部に放出されたプロセスガスは、水素分離器１、水素分離器２と筺状容器３との間の間隙を上昇しながら改質されて水素を生成する。生成水素を含むプロセスガスは、水素分離器１、水素分離器２と筺状容器３との間の間隙を上昇しながら、まず、水素分離器１のＰｄ系合金水素分離膜を透過して精製され、さらに水素分離器２の５Ａ族金属合金水素分離膜を透過して精製される。精製水素は、水素導出管５を介して取り出される。   A process gas, which is a mixed gas of raw fuel and water vapor, is introduced through the introduction pipe 4. The process gas released to the lower end in the vessel 3 is reformed while raising the gap between the hydrogen separator 1, the hydrogen separator 2 and the bowl-like vessel 3 to generate hydrogen. The process gas containing the produced hydrogen is first purified through the Pd-based alloy hydrogen separation membrane of the hydrogen separator 1 while ascending the gap between the hydrogen separator 1, the hydrogen separator 2 and the bowl-shaped vessel 3. Further, it is purified by permeating through the hydrogen separation membrane of Group 5A metal alloy of the hydrogen separator 2. Purified hydrogen is taken out through the hydrogen outlet pipe 5.

〈本発明の構成態様例３〉
図８は、本発明の構成態様例３を説明する図である。図８（ａ）は円筒状多孔質支持体周面に２種類の合金水素分離膜を設置した水素分離器１１の斜視図、図８（ｂ）は２種類の合金水素分離膜を設置した水素分離器１１とこれを収容した円筒状容器１３との断面図である。図８（ｂ）中、改質触媒層として示しているように、円筒状容器１３とそれに収容された水素分離器１１と間には改質触媒層が配置されている。 <Configuration Example 3 of the Present Invention>
FIG. 8 is a diagram for explaining a configuration aspect example 3 of the present invention. FIG. 8A is a perspective view of the hydrogen separator 11 in which two types of alloy hydrogen separation membranes are installed on the peripheral surface of the cylindrical porous support, and FIG. 8B is a hydrogen in which two types of alloy hydrogen separation membranes are installed. It is sectional drawing of the separator 11 and the cylindrical container 13 which accommodated this. As shown as a reforming catalyst layer in FIG. 8B, the reforming catalyst layer is disposed between the cylindrical vessel 13 and the hydrogen separator 11 accommodated therein.

図８（ａ）のとおり、水素分離器１１は合金からなる円筒状多孔質支持体の外周面にそれぞれ間隔を置いてＰｄ系合金水素分離膜と５Ａ族金属合金水素分離膜との２種類の合金水素分離膜を順次配置して構成される。２種類の合金水素分離膜の配置は、プロセスガス（原燃料＋水蒸気）の流れ方向でみて、まずＰｄ系合金水素分離膜を配置し、次いで５Ａ族金属合金水素分離膜を配置する。水素分離器１１と円筒状容器１３との間には改質触媒層が配置される。符号１４はプロセスガス導入管であり、円筒状容器１３の底部に開口している。   As shown in FIG. 8 (a), the hydrogen separator 11 has two types of Pd-based alloy hydrogen separation membrane and 5A group metal alloy hydrogen separation membrane spaced from each other on the outer peripheral surface of a cylindrical porous support made of an alloy. The alloy hydrogen separation membrane is sequentially arranged. As for the arrangement of the two types of alloy hydrogen separation membranes, a Pd-based alloy hydrogen separation membrane is first arranged, and then a Group 5A metal alloy hydrogen separation membrane is arranged, as viewed in the flow direction of the process gas (raw fuel + water vapor). A reforming catalyst layer is disposed between the hydrogen separator 11 and the cylindrical vessel 13. Reference numeral 14 denotes a process gas introduction pipe which opens at the bottom of the cylindrical container 13.

原燃料と水蒸気の混合ガスであるプロセスガスは、その導入管１４を介して導入される。円筒状容器１３内の下端部に放出されたプロセスガスは、水素分離器１１と円筒状容器１３との間の間隙を上昇しながら改質されて水素を生成する。生成水素を含むプロセスガスは、水素分離器１と円筒状容器３との間の間隙を上昇しながら、まず、水素分離器１のうちＰｄ系合金水素分離膜を透過して精製され、さらに５Ａ族金属合金水素分離膜を透過して精製される。精製水素は、水素導出管５を介して取り出される。プロセスガスを改質し、そのように水素を透過、精製した後のオフガス（水素を分離後の残りのガスであるプロセスガスオフガス）は導出管１６を介して排出、取り出される。   A process gas, which is a mixed gas of raw fuel and water vapor, is introduced through the introduction pipe 14. The process gas released to the lower end portion in the cylindrical container 13 is reformed while raising the gap between the hydrogen separator 11 and the cylindrical container 13 to generate hydrogen. The process gas containing the generated hydrogen is first purified through the Pd-based alloy hydrogen separation membrane in the hydrogen separator 1 while rising in the gap between the hydrogen separator 1 and the cylindrical vessel 3, and further 5A. It is refined by permeating the hydrogen separation membrane. Purified hydrogen is taken out through the hydrogen outlet pipe 5. The offgas after reforming the process gas and permeating and purifying the hydrogen in this way (process gas offgas which is the remaining gas after separating hydrogen) is discharged and taken out through the outlet pipe 16.

〈本発明の構成態様例４〉
図９は、本発明の構成態様例４を説明する図である。図９（ａ）は円筒状で、改質触媒機能を持つ多孔質支持体の外周面に２種類の合金水素分離膜を設置した水素分離器１１の斜視図、図９（ｂ）は２種類の合金水素分離膜を設置した水素分離器１１とこれを収容した円筒状容器１３との断面図である。 <Configuration Example 4 of the Present Invention>
FIG. 9 is a diagram illustrating a configuration aspect example 4 of the present invention. FIG. 9A is a perspective view of a hydrogen separator 11 which is cylindrical and has two kinds of alloy hydrogen separation membranes installed on the outer peripheral surface of a porous support having a reforming catalyst function, and FIG. It is sectional drawing of the hydrogen separator 11 which installed this alloy hydrogen separation membrane, and the cylindrical container 13 which accommodated this.

図９（ａ）のとおり、水素分離器１１は合金からなる改質触媒機能を持つ円筒状多孔質支持体の外周面にそれぞれ間隔を置いてＰｄ系合金水素分離膜と５Ａ族金属合金水素分離膜との２種類の合金水素分離膜を順次配置して構成される。２種類の合金水素分離膜の配置は、プロセスガス（原燃料＋水蒸気）の流れ方向でみて、まずＰｄ系合金水素分離膜を配置し、次いで５Ａ族金属合金水素分離膜を配置する。   As shown in FIG. 9 (a), the hydrogen separator 11 has a Pd-based alloy hydrogen separation membrane and a 5A group metal alloy hydrogen separation spaced from each other on the outer peripheral surface of a cylindrical porous support made of an alloy and having a reforming catalyst function. Two types of alloy hydrogen separation membranes with the membrane are sequentially arranged. As for the arrangement of the two types of alloy hydrogen separation membranes, a Pd-based alloy hydrogen separation membrane is first arranged, and then a Group 5A metal alloy hydrogen separation membrane is arranged, as viewed in the flow direction of the process gas (raw fuel + water vapor).

円筒状の改質触媒機能を持つ多孔質支持体における円筒状の内空にはプロセスガス（原燃料＋水蒸気）の導入管１４が配置されている。原燃料と水蒸気の混合ガスであるプロセスガスは、その導入管１４を介して導入される。導入管１４は下端で開口しているので、プロセスガスは当該開口端で折り返し、導入管１４と円筒状多孔質支持体との間の間隙を上昇しながら、多孔質支持体の改質触媒機能により改質されて水素を生成する。   A process gas (raw fuel + water vapor) introduction pipe 14 is disposed in a cylindrical inner space of the porous support having a cylindrical reforming catalyst function. A process gas, which is a mixed gas of raw fuel and water vapor, is introduced through the introduction pipe 14. Since the introduction pipe 14 is opened at the lower end, the process gas is turned back at the opening end, and while the gap between the introduction pipe 14 and the cylindrical porous support is raised, the reforming catalyst function of the porous support is achieved. To produce hydrogen.

生成水素を含むプロセスガスは、水素分離器１とプロセスガス導入管１４との間の間隙を上昇しながら、まず、水素分離器１のうちＰｄ系合金水素分離膜を透過して精製され、さらに５Ａ族金属合金水素分離膜を透過して精製される。精製水素は、水素分離器１と円筒状容器１３との間に流入し水素導出管１５を介して取り出される。   The process gas containing the produced hydrogen is first purified through the Pd-based alloy hydrogen separation membrane in the hydrogen separator 1 while raising the gap between the hydrogen separator 1 and the process gas introduction pipe 14. It is purified by permeating through a 5A group metal alloy hydrogen separation membrane. Purified hydrogen flows between the hydrogen separator 1 and the cylindrical container 13 and is taken out via the hydrogen outlet pipe 15.

１、２、１１ 水素分離器
３ 筺状容器
１３ 円筒状容器
４、１４ プロセスガス（原燃料＋水蒸気）の導入管
５、１５ 水素導出管
１６ プロセスガスオフガス導出管
1, 2, 11 Hydrogen separator 3 Casket-shaped vessel 13 Cylindrical vessel 4, 14 Process gas (raw fuel + water vapor) introduction pipe 5, 15 Hydrogen lead-out pipe 16 Process gas off-gas lead-out pipe

Claims (4)

水素分離膜を支持する役割を果たす円筒状の多孔質支持体もしくは多孔板からなる支持体の外周面に前記水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器。 The hydrogen separation membrane disposed on the outer peripheral surface of the support consisting serves cylindrical porous support or the porous plate for supporting the hydrogen separation membrane, and placing the reforming catalyst layer to the outer periphery of the hydrogen separation membrane a consisting of hydrogen separation type reformer, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, 0.10MP a absolute pressure on the downstream side of the gas to be treated two-stage hydrogen separation reformer which characterized by using a V alloy or Ta alloy hydrogen separation membrane can be used without causing brittle fracture on the following. 改質触媒としての役割と水素分離膜を支持する役割を同時に果たす円筒状の改質触媒兼多孔質支持体の外周面に前記水素分離膜を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器。 A hydrogen separation type reformer which is formed by placing the hydrogen separation membrane to the outer peripheral surface of a cylindrical reforming catalyst and porous support serves to support the role and the hydrogen separation membrane as the reforming catalyst at the same time , the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, the downstream side of the gas to be treated can be used without causing brittle fracture at 0.10MP a than on the absolute pressure A two-stage hydrogen separation reformer characterized by using a V alloy or Ta alloy hydrogen separation membrane. 水素分離膜を支持する役割を果たす筺状の多孔質支持体もしくは多孔板からなる支持体の外周面に前記水素分離膜を配置し、当該水素分離膜の外周に改質触媒層を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器。 The hydrogen separation membrane disposed on the outer peripheral surface of the support made of porous support or the porous plate serves enclosure for supporting the hydrogen separation membrane, and placing the reforming catalyst layer to the outer periphery of the hydrogen separation membrane a consisting of hydrogen separation type reformer, the hydrogen separation membrane, the upstream side of the gas to be treated with a Pd-based alloy hydrogen separation membrane, 0.10MP a absolute pressure on the downstream side of the gas to be treated two-stage hydrogen separation reformer which characterized by using a V alloy or Ta alloy hydrogen separation membrane can be used without causing brittle fracture on the following. 改質触媒としての役割と水素分離膜を支持する役割を同時に果たす筺状の改質触媒兼支持体の外周面に前記水素分離膜を配置してなる水素分離型改質器であって、前記水素分離膜は、被処理ガスの上流側にはＰｄ系合金水素分離膜を用い、前記被処理ガスの下流側には絶対圧で０．１０ＭＰａ以上でも脆性破壊をおこさず使用できるＶ合金又はＴａ合金水素分離膜を用いてなることを特徴とする２段式水素分離型改質器。 A hydrogen separation type reformer which is formed by placing the hydrogen separation membrane roles and hydrogen separation membrane as the reforming catalyst on the outer peripheral surface of the reforming catalyst and support enclosure that serves to support at the same time, the hydrogen separation membrane using a Pd alloy hydrogen separation membrane on the upstream side of the gas to be treated, the V alloy that can be used without causing an absolute pressure brittle fracture even on 0.10MP a than at the downstream side of the gas to be treated Alternatively, a two-stage hydrogen separation reformer characterized by using a Ta alloy hydrogen separation membrane.
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