JP2014234322A - Hydrogen production apparatus stopping method and hydrogen production apparatus - Google Patents

Hydrogen production apparatus stopping method and hydrogen production apparatus Download PDF

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JP2014234322A
JP2014234322A JP2013115731A JP2013115731A JP2014234322A JP 2014234322 A JP2014234322 A JP 2014234322A JP 2013115731 A JP2013115731 A JP 2013115731A JP 2013115731 A JP2013115731 A JP 2013115731A JP 2014234322 A JP2014234322 A JP 2014234322A
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行伸 谷口
Yukinobu Taniguchi
行伸 谷口
彰利 藤澤
Akitoshi Fujisawa
彰利 藤澤
脩平 留川
Shuhei Tomekawa
脩平 留川
真一 三浦
Shinichi Miura
真一 三浦
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Kobe Steel Ltd
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PROBLEM TO BE SOLVED: To provide a hydrogen production apparatus stopping method and a hydrogen production apparatus that can shorten the time necessary to completely stop the apparatus while preventing the deterioration of a catalyst in a reformer, and that can reduce the apparatus in size.SOLUTION: This invention provides a stopping method for a hydrogen production apparatus comprising a reformer having a modification section for generating modified gas containing hydrogen and carbon monoxide by steam modification of a hydrocarbon-containing feed gas, and a conversion section for discharging hydrogen-rich converted gas by CO conversion of the modified gas, characterized in that the hydrogen production apparatus further comprises a water electrolysis unit and the supply of the feed gas and the steam to the modifier is stopped as well as the inside of the modifier is purged by the hydrogen gas generated in the water electrolysis unit. This invention also provides a hydrogen production apparatus comprising a modifier for discharging hydrogen-rich converted gas, a water electrolysis unit, and control means for stopping the supply of feed gas and steam to the modifies as well as for purging the inside of the modifier by the hydrogen gas generated in the water electrolysis unit.

Description

本発明は、水素製造装置の停止方法及び水素製造装置に関する。   The present invention relates to a method for stopping a hydrogen production apparatus and a hydrogen production apparatus.

近年、地球環境の改善につながる燃料電池用の燃料として、水素への期待が高まっている。水素製造方法の代表的なものとしては、炭化水素（天然ガス）を燃料とした水蒸気改質法が挙げられる。この水蒸気改質法では、改質器で改質反応及び変成反応によって天然ガスから水素を多く含む改質ガスを生成し、この改質ガスに含まれる水素以外の不純物を改質器の後段に設置される水素精製器で除去する。この水素精製器としては、ＰＳＡ（Ｐｒｅｓｓｕｒｅ Ｓｗｉｎｇ Ａｄｓｏｒｐｔｉｏｎ）方式のものや、水素吸蔵合金方式のものが挙げられる。   In recent years, there is an increasing expectation for hydrogen as a fuel for fuel cells that leads to improvement of the global environment. A typical hydrogen production method is a steam reforming method using hydrocarbon (natural gas) as a fuel. In this steam reforming method, reforming gas containing a large amount of hydrogen is generated from natural gas by reforming reaction and transformation reaction in the reformer, and impurities other than hydrogen contained in this reformed gas are placed downstream of the reformer. Remove with installed hydrogen purifier. Examples of the hydrogen purifier include a PSA (Pressure Swing Adsorption) type and a hydrogen storage alloy type.

上記水素製造装置において、水素の製造を停止する場合、上記改質器への炭化水素を含む原料ガス及び水蒸気の供給を停止することで改質ガスの生成を停止させる。このとき停止後の改質器において、原料ガスが残留していると熱分解により炭素が触媒層に析出し触媒活性が低下する。そこで、一般には原料ガス停止後、改質器内を水蒸気でパージ（置換）した後、さらにこの水蒸気を不活性ガスでパージする方法が従来から用いられている。このように原料ガスをパージした水蒸気をさらに不活性ガスでパージするのは、改質器内の温度が低下した際、水蒸気の水分凝縮による酸化や結露によって触媒が劣化するのを防ぐためである。   In the hydrogen production apparatus, when the production of hydrogen is stopped, the generation of the reformed gas is stopped by stopping the supply of the raw material gas containing hydrocarbons and the water vapor to the reformer. At this time, if the raw material gas remains in the reformer after stopping, carbon is deposited on the catalyst layer due to thermal decomposition and the catalytic activity is lowered. Therefore, generally, a method of purging (replacement) the interior of the reformer with steam after stopping the raw material gas and further purging the steam with an inert gas has been conventionally used. The reason why the water vapor purged with the raw material gas is further purged with an inert gas is to prevent the catalyst from deteriorating due to oxidation or condensation due to moisture condensation of water vapor when the temperature in the reformer decreases. .

上記不活性ガスでパージする方法の場合、不活性ガスの貯蔵及び供給設備が別途必要となる。そこで、不活性ガスの代わりに原料ガスで改質器内を再度パージする方法が提案されている（特許第３９７００６４号）。この方法は、水蒸気で改質器内をパージした後、原料ガスが熱分解しない温度まで改質器内温度が低下した後に原料ガスで再度パージを行うものである。   In the case of the purge method using the inert gas, an inert gas storage and supply facility is required separately. Therefore, a method has been proposed in which the inside of the reformer is purged again with a raw material gas instead of an inert gas (Japanese Patent No. 3970064). In this method, after purging the inside of the reformer with water vapor, the temperature inside the reformer is lowered to a temperature at which the raw material gas is not thermally decomposed, and then purging is performed again with the raw material gas.

また、不活性ガスの代わりに原料ガスの脱硫時に発生した水素ガスを用いて水蒸気の再パージを行う方法も提案されている（特開２００７−７０５０２号）。   In addition, a method of repurging water vapor using hydrogen gas generated during desulfurization of the raw material gas instead of the inert gas has been proposed (Japanese Patent Laid-Open No. 2007-70502).

しかしながら、上記の原料ガスで再パージを行う従来技術は、改質器内温度が４００℃程度以下になるまで待機する時間が必要であるため、装置の停止が完了するまでの時間が長くなる。特に、改質器の容量が１０Ｎｍ３／ｈ以上になると、触媒温度が定格時の約７００℃から４００℃程度まで低下するのには数時間を要する。また、原料ガスを供給する前に改質器内温度が低下しすぎると水蒸気の凝縮が発生するリスクが生じる。一方で、上記の脱硫時発生水素ガスを用いて再パージを行う従来技術は、脱硫で発生する水素ガスにメタンが含有され易いため、このメタンによって改質器内に炭素析出が生じるおそれがある。また、脱硫時に発生した水素ガスを停止時まで貯蔵しておくホルダや圧送用のポンプ等が必要となるため、設備の大型化が避けられない。 However, in the conventional technique in which the above-described raw material gas is re-purged, it is necessary to wait for the reformer temperature to be about 400 ° C. or lower, so that it takes a long time to stop the apparatus. In particular, when the capacity of the reformer is 10 Nm 3 / h or more, it takes several hours for the catalyst temperature to drop from about 700 ° C. at the rated time to about 400 ° C. In addition, if the temperature inside the reformer is too low before the raw material gas is supplied, there is a risk that condensation of water vapor occurs. On the other hand, in the conventional technique in which re-purging is performed using the hydrogen gas generated at the time of desulfurization, methane is easily contained in the hydrogen gas generated by desulfurization. Therefore, carbon deposition may occur in the reformer due to the methane. . Moreover, since a holder for storing the hydrogen gas generated at the time of desulfurization until the stoppage, a pump for pumping, and the like are necessary, an increase in size of the facility is inevitable.

特許第３９７００６４号公報Japanese Patent No. 3970064 特開２００７−７０５０２号公報JP 2007-70502 A

本発明は、前述のような事情に基づいてなされたものであり、改質器内の触媒の劣化を防止しつつ、装置が完全に停止するまでの時間を短縮化でき、かつ装置を小型化できる水素製造装置の停止方法、及び水素製造装置の提供を目的とする。   The present invention has been made based on the circumstances as described above, and can prevent the catalyst in the reformer from deteriorating, shorten the time until the apparatus is completely stopped, and downsize the apparatus. An object of the present invention is to provide a method for stopping a hydrogen production apparatus and a hydrogen production apparatus.

上記課題を解決するためになされた発明は、
炭化水素含有原料ガスの水蒸気改質により水素及び一酸化炭素を含む改質ガスを生成する改質部と、この改質ガスのＣＯ変成により水素リッチな変成ガスを排出する変成部とを有する改質器を備える水素製造装置の停止方法であって、
上記水素製造装置が水電解装置をさらに備え、
上記改質器への原料ガス及び水蒸気の供給を停止すると共に、上記水電解装置で発生した水素ガスにより上記改質器内をパージすることを特徴とする。 The invention made to solve the above problems is
A reforming section that generates reformed gas containing hydrogen and carbon monoxide by steam reforming of the hydrocarbon-containing source gas, and a reforming section that discharges hydrogen-rich modified gas by CO conversion of the reformed gas. A method for stopping a hydrogen production apparatus including a quality device,
The hydrogen production apparatus further comprises a water electrolysis device,
The supply of raw material gas and water vapor to the reformer is stopped, and the interior of the reformer is purged with hydrogen gas generated by the water electrolysis apparatus.

当該水素製造装置の停止方法においては、水電解装置で発生した水素ガスで改質器内をパージ（置換）する。この水素ガスは純度が高く改質器内が高温であっても炭素の析出が起こらないため、従来の方法のように改質器内の温度が低下することを待たずに改質器内をパージすることができる。その結果、改質器内の触媒の劣化を防止しつつ、装置の停止までの時間を短縮化できる。さらに、水素製造装置の停止時に上記水電解装置で必要量の水素ガスを発生させることができ、水素ガスをあらかじめ貯蓄しておく設備等が不要となるため、水素製造装置の小型化が可能となる。さらに、当該水素製造装置の停止方法は、高純度の水素ガスで改質器内を充填するため、酸化した改質器内の触媒を水素ガスによって還元する効果も得ることができる。   In the method for stopping the hydrogen production apparatus, the interior of the reformer is purged (replaced) with hydrogen gas generated by a water electrolysis apparatus. Since this hydrogen gas has a high purity and carbon deposition does not occur even when the temperature inside the reformer is high, it does not wait for the temperature inside the reformer to decrease as in the conventional method. Can be purged. As a result, it is possible to shorten the time until the apparatus is stopped while preventing deterioration of the catalyst in the reformer. Furthermore, when the hydrogen production apparatus is stopped, the water electrolysis apparatus can generate a necessary amount of hydrogen gas, which eliminates the need to store hydrogen gas in advance, and the hydrogen production apparatus can be downsized. Become. Further, since the method for stopping the hydrogen production apparatus fills the reformer with high-purity hydrogen gas, it is possible to obtain an effect of reducing the oxidized catalyst in the reformer with hydrogen gas.

また、上記課題を解決するためになされた別の発明は、
炭化水素含有原料ガスの水蒸気改質により水素及び一酸化炭素を含む改質ガスを生成する改質部と、この改質ガスのＣＯ変成により水素リッチな変成ガスを排出する変成部とを有する改質器を備える水素製造装置であって、
水電解装置と、
上記改質器への原料ガス及び水蒸気の供給を停止すると共に、上記水電解装置で発生した水素ガスにより上記改質器内をパージする制御手段と
をさらに備えることを特徴とする。 Moreover, another invention made in order to solve the said subject is:
A reforming section that generates reformed gas containing hydrogen and carbon monoxide by steam reforming of the hydrocarbon-containing source gas, and a reforming section that discharges hydrogen-rich modified gas by CO conversion of the reformed gas. A hydrogen production apparatus comprising a quality device,
A water electrolysis device,
And a control means for purging the interior of the reformer with hydrogen gas generated by the water electrolysis device while stopping the supply of the raw material gas and water vapor to the reformer.

当該水素製造装置は、上述のように水電解装置で発生した水素ガスで改質器内をパージすることで、改質器内の触媒の劣化を防止しつつ、装置の停止までの時間を短縮化できると共に、水素ガスをあらかじめ貯蓄しておく設備等が不要となるため、装置の小型化が可能となる。   The hydrogen production device purges the interior of the reformer with the hydrogen gas generated in the water electrolysis device as described above, thereby preventing deterioration of the catalyst in the reformer and shortening the time until the device is stopped. In addition, since the equipment for storing hydrogen gas in advance is not necessary, the apparatus can be miniaturized.

上記改質器が酸素含有ガスの酸化により改質反応に必要な熱を得る自己熱型の改質器であり、上記酸素含有ガスとして上記水電解装置で発生した酸素ガスを改質器に供給するとよい。このように改質器を自己熱型とし、この改質器に水電解装置で水素を生成する際に発生する酸素ガスを供給することで、改質器を加熱する設備や、改質器に供給するための酸素ガスを生成又は貯蔵する設備を小型化又は省略することができるため、当該水素製造装置をさらに小型化することができる。   The reformer is a self-heating reformer that obtains the heat required for the reforming reaction by oxidizing the oxygen-containing gas, and supplies the reformer with oxygen gas generated by the water electrolysis device as the oxygen-containing gas. Good. In this way, the reformer is a self-heating type, and oxygen gas generated when hydrogen is generated by the water electrolysis device is supplied to the reformer, thereby heating the reformer and the reformer. Since equipment for generating or storing oxygen gas to be supplied can be downsized or omitted, the hydrogen production apparatus can be further downsized.

上記変成ガス中の水素以外のガスをＰＳＡ方式によって吸着する吸着塔を有する水素精製器をさらに備え、上記吸着塔の洗浄及び／又は昇圧に上記水電解装置で発生した水素ガスを用いるとよい。このように当該水素製造装置にＰＳＡ方式の水素精製器を用いる場合、この水素精製器が有する吸着塔の洗浄及び／又は昇圧に上記水電解装置で発生した高純度の水素ガスを用いることで、吸着塔内の純度を向上させて当該水素製造装置で得られる製品水素ガスの純度を高めることができる。また、製品水素ガスの純度が向上することによって、吸着塔を小型化することができるため、吸着塔の圧力変動を低減して水素製造効率を向上させることができる。さらにこの吸着塔の小型化は、当該水素製造装置の一層の小型化に寄与する。   A hydrogen purifier having an adsorption tower that adsorbs a gas other than hydrogen in the metamorphic gas by the PSA method may be further provided, and hydrogen gas generated by the water electrolysis apparatus may be used for cleaning and / or boosting the adsorption tower. Thus, when using a PSA-type hydrogen purifier in the hydrogen production apparatus, by using the high-purity hydrogen gas generated in the water electrolysis apparatus for cleaning and / or boosting the adsorption tower of the hydrogen purifier, The purity of the product hydrogen gas obtained by the hydrogen production apparatus can be increased by improving the purity in the adsorption tower. Further, since the purity of the product hydrogen gas is improved, the adsorption tower can be reduced in size, so that the pressure fluctuation of the adsorption tower can be reduced and the hydrogen production efficiency can be improved. Further, the downsizing of the adsorption tower contributes to further downsizing of the hydrogen production apparatus.

以上説明したように、本発明の水素製造装置の停止方法及び水素製造装置は、改質器内の触媒の劣化を防止しつつ、装置が完全に停止するまでの時間を短縮化でき、かつ装置を小型化できる。つまり、本発明の水素製造装置の停止方法及び水素製造装置によれば、任意のタイミングで水素パージを開始することができ、また炭素析出や水蒸気凝縮による触媒の劣化を防止でき、さらに不活性ガスのガスホルダ等の追加の設備を不要とすることができる。   As described above, the method for stopping a hydrogen production apparatus and the hydrogen production apparatus of the present invention can shorten the time until the apparatus completely stops while preventing deterioration of the catalyst in the reformer, and the apparatus. Can be miniaturized. That is, according to the method for stopping a hydrogen production apparatus and the hydrogen production apparatus of the present invention, hydrogen purge can be started at an arbitrary timing, catalyst deterioration due to carbon deposition and water vapor condensation can be prevented, and an inert gas can be prevented. Additional equipment such as a gas holder can be eliminated.

本発明の一実施形態に係る水素製造装置を示す概略図Schematic which shows the hydrogen production apparatus which concerns on one Embodiment of this invention. 図１の水素製造装置が有する水素精製器を示す概略図Schematic showing the hydrogen purifier of the hydrogen production apparatus of FIG. 本発明の一実施形態に係る水素製造装置の停止方法のフローチャートThe flowchart of the stop method of the hydrogen production device concerning one embodiment of the present invention 図３の水素製造装置の停止方法とは異なる実施形態に係る水素製造装置の停止方法のフローチャートThe flowchart of the stop method of the hydrogen production apparatus which concerns on embodiment different from the stop method of the hydrogen production apparatus of FIG. 図３及び図４の水素製造装置の停止方法とは異なる実施形態に係る水素製造装置の停止方法のフローチャートFlowchart of the hydrogen production apparatus stop method according to an embodiment different from the hydrogen production apparatus stop method of FIGS. 3 and 4

以下、適宜図面を参照しつつ本発明の水素製造装置及び水素製造装置の停止方法の実施形態を詳説する。   Hereinafter, embodiments of a hydrogen production apparatus and a hydrogen production apparatus stop method of the present invention will be described in detail with reference to the drawings as appropriate.

＜水素製造装置＞
図１の水素製造装置１は、炭化水素含有原料ガスＡの水蒸気改質により水素及び一酸化炭素を含む改質ガスを生成する改質部及びこの改質ガスのＣＯ変成により水素リッチな改質ガスＣを排出する変成部を有する改質器２と、改質ガスＣ中の水素以外のガスをＰＳＡによって吸着する水素精製工程を行う水素精製器３と、水電解により高純度水素ガスＦ及び酸素ガスＧを発生する水電解装置４と、制御手段（図示せず）とを備える。 <Hydrogen production equipment>
The hydrogen production apparatus 1 in FIG. 1 includes a reforming unit that generates a reformed gas containing hydrogen and carbon monoxide by steam reforming of a hydrocarbon-containing raw material gas A, and a hydrogen-rich reforming by CO conversion of the reformed gas. A reformer 2 having a shift section that discharges gas C; a hydrogen purifier 3 that performs a hydrogen purification step of adsorbing a gas other than hydrogen in reformed gas C by PSA; and high-purity hydrogen gas F and water by electrolysis A water electrolysis device 4 that generates oxygen gas G and a control means (not shown) are provided.

上記改質器２は、酸素含有ガスの酸化により後述する改質反応に必要な熱を得る自己熱型の改質器（オートサーマル型改質器）である。この改質器２には、上記原料ガスＡが原料ガス供給ライン１０から供給される他に、改質用の水蒸気Ｂが水蒸気供給ライン１１から供給され、さらに水電解装置４から発生する酸素ガスＧが酸素ガス供給ライン１５によって供給される。   The reformer 2 is a self-heating reformer (autothermal reformer) that obtains heat necessary for a reforming reaction described later by oxidizing an oxygen-containing gas. In addition to the raw material gas A being supplied from the raw material gas supply line 10, the reformer 2 is supplied with reforming steam B from the steam supply line 11, and oxygen gas generated from the water electrolysis device 4. G is supplied by the oxygen gas supply line 15.

上記原料ガスＡとしては、天然ガス等の炭化水素を含有するガスを用いることができる。上記改質器２における原料ガスＡの水蒸気改質及びＣＯ変成は、それぞれ以下の化学式で表される改質反応及び変成反応で構成される。
（１）改質反応
ＣｎＨｍ＋ｎＨ２Ｏ→ｎＣＯ＋（ｍ／２＋ｎ）Ｈ２
（２）変成反応
ＣＯ＋Ｈ２Ｏ→ＣＯ２＋Ｈ２ As the source gas A, a gas containing a hydrocarbon such as natural gas can be used. Steam reforming and CO conversion of the raw material gas A in the reformer 2 are constituted by a reforming reaction and a conversion reaction represented by the following chemical formulas, respectively.
(1) reforming reaction C n H m + nH 2 O → nCO + (m / 2 + n) H 2
(2) Metamorphic reaction CO + H 2 O → CO 2 + H 2

改質器２では、原料ガス供給ライン１０から供給される原料ガスＡを改質部で改質反応により水蒸気Ｂで改質して水素及び一酸化炭素を主成分とするガスとした後（上記式（１））、さらに変成部でこのガスを水蒸気Ｂで変成し水素リッチな改質ガスＣを生成し排出する（上記式（２））。また、改質器２では、水電解装置４で発生した酸素ガスＧと原料ガスＡとの酸化反応に伴う発熱によって吸熱反応である上記改質反応が促進される。上記改質ガスＣ中には、水素の他、一酸化炭素、二酸化炭素、メタン等の未反応の天然ガス成分、水などの不純物が含まれる。   In the reformer 2, after the raw material gas A supplied from the raw material gas supply line 10 is reformed with steam B by a reforming reaction in the reforming section to be a gas mainly composed of hydrogen and carbon monoxide (the above-mentioned Further, this gas is transformed with water vapor B at the transformation section to produce and discharge a hydrogen-rich reformed gas C (formula (2) above). In the reformer 2, the reforming reaction, which is an endothermic reaction, is promoted by the heat generated by the oxidation reaction between the oxygen gas G and the raw material gas A generated in the water electrolysis apparatus 4. The reformed gas C contains hydrogen, unreacted natural gas components such as carbon monoxide, carbon dioxide, and methane, and impurities such as water.

改質器２から排出される改質ガスＣは、改質ガス供給ライン１２を通して水素精製器３に供給される。ただし、当該水素製造装置１の起動直後、すなわち改質器２への原料ガスＡの供給開始直後は、改質器２内の温度が低く、吸熱反応である改質反応の進行が鈍く水素濃度の低い改質ガスＣが排出される。この水素濃度の低い改質ガスＣは改質ガス回収ライン１３を通してオフガスとして回収される。   The reformed gas C discharged from the reformer 2 is supplied to the hydrogen purifier 3 through the reformed gas supply line 12. However, immediately after the start-up of the hydrogen production apparatus 1, that is, immediately after the start of the supply of the raw material gas A to the reformer 2, the temperature in the reformer 2 is low and the reforming reaction, which is an endothermic reaction, proceeds slowly and the hydrogen concentration is low. A low reformed gas C is discharged. The reformed gas C having a low hydrogen concentration is recovered as off-gas through the reformed gas recovery line 13.

上記水素精製器３は、図２に示すように改質ガスＣ中の上記不純物を吸着する吸着剤を充填した複数の吸着塔５ａ，５ｂ，５ｃを有し、高純度の水素ガスＤを排出する。これらの吸着塔５ａ，５ｂ，５ｃは、それぞれ吸着、減圧、洗浄、昇圧、吸着の一連の工程を順次切り替えて運転される。吸着塔内の圧力を減圧する工程及び高純度水素ガスＦで洗浄する工程により、吸着した不純物を除去し、吸着塔内の吸着剤が再生される。その後、吸着剤を再生した吸着塔を再び昇圧し水素精製に再び供する。当該水素製造装置１の運転中、いずれかの吸着塔が吸着工程となるように上記一連の工程をずらして切り替えることで、吸着と再生とを異なる吸着塔で同時に行うことが可能となり、連続的に水素ガスＤを製造できる。   The hydrogen purifier 3 has a plurality of adsorption towers 5a, 5b, 5c filled with an adsorbent that adsorbs the impurities in the reformed gas C as shown in FIG. To do. These adsorption towers 5a, 5b, and 5c are operated by sequentially switching a series of steps of adsorption, depressurization, washing, pressurization, and adsorption. The adsorbed impurities are removed and the adsorbent in the adsorption tower is regenerated by reducing the pressure in the adsorption tower and washing with the high purity hydrogen gas F. Thereafter, the adsorption tower in which the adsorbent has been regenerated is pressurized again and subjected to hydrogen purification again. During the operation of the hydrogen production apparatus 1, it is possible to perform adsorption and regeneration simultaneously in different adsorption towers by shifting the above series of steps so that one of the adsorption towers becomes an adsorption step, and continuously. Hydrogen gas D can be produced.

吸着塔５ａ，５ｂ，５ｃには、改質ガスＣの主な不純物である一酸化炭素、二酸化炭素及びメタンを吸着可能な吸着剤が充填される。この吸着剤は各不純物をＰＳＡで吸着可能なものであれば特に限定されない。メタンと二酸化炭素との双方を吸着可能な吸着剤としては、炭素系の吸着剤を挙げることができ、具体的には例えば活性炭、ＣＭＳ（カーボンモレキュラーシーブ）等を用いることができる。また、一酸化炭素の吸着剤としては、例えばゼオライト、シリカ、アルミナ、ポリスチレン系樹脂等を用いることができるが、特に多孔質シリカ、多孔質アルミナ、ポリスチレン系樹脂のうち１種以上の担体に、ハロゲン化銅（Ｉ）及び／又はハロゲン化銅（ＩＩ）を担持させた材料、又はこの材料を還元処理したものを用いることが好ましい。このような材料は、一酸化炭素の吸着性能が大きいため、吸着剤使用量を削減できると共に、水素回収率の向上を図ることが出来る。   The adsorption towers 5a, 5b, and 5c are filled with an adsorbent capable of adsorbing carbon monoxide, carbon dioxide, and methane, which are main impurities of the reformed gas C. This adsorbent is not particularly limited as long as each impurity can be adsorbed by PSA. Examples of the adsorbent capable of adsorbing both methane and carbon dioxide include carbon-based adsorbents, and specifically, for example, activated carbon, CMS (carbon molecular sieve) and the like can be used. Further, as the carbon monoxide adsorbent, for example, zeolite, silica, alumina, polystyrene-based resin, etc. can be used. Particularly, one or more kinds of carriers among porous silica, porous alumina, polystyrene-based resin, It is preferable to use a material supporting copper (I) halide and / or copper (II) halide, or a material obtained by reducing this material. Since such a material has a large carbon monoxide adsorption performance, the amount of adsorbent used can be reduced and the hydrogen recovery rate can be improved.

改質ガス導入ライン１０１は改質器２から排出された改質ガスＣを水素精製器３へ導入するためのラインである。改質ガス導入ライン１０１と３つの吸着塔５ａ，５ｂ，５ｃとはそれぞれ改質ガス導入弁Ｖ１０１，Ｖ１０２，Ｖ１０３を介して接続される。   The reformed gas introduction line 101 is a line for introducing the reformed gas C discharged from the reformer 2 into the hydrogen purifier 3. The reformed gas introduction line 101 and the three adsorption towers 5a, 5b, 5c are connected via reformed gas introduction valves V101, V102, V103, respectively.

オフガス排出ライン１０２は吸着塔５ａ，５ｂ，５ｃ内を減圧するために用いるラインである。オフガス排出ライン１０２は、３つの吸着塔５ａ，５ｂ，５ｃとオフガス排出弁Ｖ１０４，Ｖ１０５，Ｖ１０６をそれぞれ介して接続される。このオフガス排出ライン１０２の下流には吸着塔５ａ，５ｂ，５ｃの再生時に大気圧以下まで減圧するための真空ポンプ（図示せず）が接続される。   The off-gas discharge line 102 is a line used for depressurizing the inside of the adsorption towers 5a, 5b, and 5c. The off-gas discharge line 102 is connected to the three adsorption towers 5a, 5b, and 5c and the off-gas discharge valves V104, V105, and V106, respectively. Downstream of the off-gas discharge line 102 is connected a vacuum pump (not shown) for reducing the pressure to below atmospheric pressure when the adsorption towers 5a, 5b, 5c are regenerated.

吸着塔５ａ，５ｂ，５ｃの再生時の排出ガスは、オフガス排出ライン１０２からオフガスＥとして排出される。   The exhaust gas at the time of regeneration of the adsorption towers 5a, 5b, 5c is discharged as off-gas E from the off-gas discharge line 102.

水素ガス回収ライン１０３は吸着塔５ａ，５ｂ，５ｃで改質ガスＣの不純物を除去して得た水素ガスＤの回収ラインであり、３つの吸着塔５ａ，５ｂ，５ｃとはそれぞれ水素ガス回収弁Ｖ１０７，Ｖ１０８，Ｖ１０９を介して接続される。回収した水素ガスＤはバッファタンク等に一時的に貯蔵され、適宜使用に供される。なお、当該水素製造装置１の起動後、水素純度が安定する（一定値に達する）前の水素ガスＤは、オフガスＥとして回収される。   The hydrogen gas recovery line 103 is a recovery line for hydrogen gas D obtained by removing impurities of the reformed gas C in the adsorption towers 5a, 5b, and 5c. The three adsorption towers 5a, 5b, and 5c are respectively hydrogen gas recovery lines. They are connected via valves V107, V108, V109. The recovered hydrogen gas D is temporarily stored in a buffer tank or the like and used as appropriate. Note that the hydrogen gas D before the hydrogen purity is stabilized (reached a certain value) after the hydrogen production apparatus 1 is started is recovered as off-gas E.

高純度水素ガス供給ライン１４は水電解装置４で水電解により発生した高純度水素ガスＦを各吸着塔に供給するラインであり、３つの吸着塔５ａ，５ｂ，５ｃとはそれぞれ水素ガス供給弁Ｖ１１０，Ｖ１１１，Ｖ１１２を介して接続される。この高純度水素ガス供給ライン１４から供給される高純度水素ガスＦは、各吸着塔の洗浄及び昇圧に用いられる。   The high-purity hydrogen gas supply line 14 is a line for supplying high-purity hydrogen gas F generated by water electrolysis in the water electrolysis apparatus 4 to each adsorption tower, and the three adsorption towers 5a, 5b, and 5c are respectively hydrogen gas supply valves. They are connected via V110, V111, and V112. The high-purity hydrogen gas F supplied from the high-purity hydrogen gas supply line 14 is used for cleaning and boosting each adsorption tower.

各吸着塔には上記水素ガス回収ライン１０３が上記水素ガス回収弁を介して接続され、高純度水素ガス供給ライン１４が上記水素ガス供給弁を介して接続されているため、１つの吸着塔から水素ガスＤを回収しながら、他の１つの吸着塔に対して高純度水素ガスＦを供給して、洗浄及び昇圧を行うことができる。例えば第一の吸着塔５ａがこれから再生工程に入る場合、第二の吸着塔５ｂに改質ガスＣが供給され、不純物が除去された水素ガスＤが第二の吸着塔５ｂの水素ガス回収弁Ｖ１０８を通して水素ガス回収ライン１０３から回収され続ける。一方で、第一の吸着塔５ａでは、第一の吸着塔５ａ内のガスを第一の吸着塔５ａのオフガス排出弁Ｖ１０４を通して排出することで第一の吸着塔５ａを減圧した後、水素ガス供給弁Ｖ１１０から高純度水素ガスＦを第一の吸着塔５ａに供給することにより、第一の吸着塔５ａの洗浄及び昇圧が行われる。この第一の吸着塔５ａの洗浄中はオフガス排出弁Ｖ１０４を通して不純物を含んだガスをオフガスＥとして排出する。一方、第三の吸着塔５ｃでは改質ガス導入弁Ｖ１０３を開けることにより改質ガスＣを導入して改質ガスＣの不純物の吸着除去を開始する。なお、適宜バッファタンクを設け高純度水素ガスＦを貯留し、このバッファタンクから高純度水素ガスＦを供給して各吸着塔の洗浄及び昇圧を行ってもよい。   The hydrogen gas recovery line 103 is connected to each adsorption tower via the hydrogen gas recovery valve, and the high-purity hydrogen gas supply line 14 is connected via the hydrogen gas supply valve. While recovering the hydrogen gas D, the high-purity hydrogen gas F can be supplied to the other one adsorption tower to perform washing and pressure increase. For example, when the first adsorption tower 5a enters the regeneration process, the reformed gas C is supplied to the second adsorption tower 5b, and the hydrogen gas D from which impurities have been removed is the hydrogen gas recovery valve of the second adsorption tower 5b. Recovery from the hydrogen gas recovery line 103 continues through V108. On the other hand, in the first adsorption tower 5a, the gas in the first adsorption tower 5a is discharged through the off-gas discharge valve V104 of the first adsorption tower 5a to depressurize the first adsorption tower 5a, and then the hydrogen gas By supplying the high-purity hydrogen gas F from the supply valve V110 to the first adsorption tower 5a, the first adsorption tower 5a is cleaned and boosted. During the cleaning of the first adsorption tower 5a, the gas containing impurities is discharged as off-gas E through the off-gas discharge valve V104. On the other hand, in the third adsorption tower 5c, the reformed gas C is introduced by opening the reformed gas introduction valve V103, and the adsorption removal of the impurities of the reformed gas C is started. A buffer tank may be provided as appropriate to store the high-purity hydrogen gas F, and the high-purity hydrogen gas F may be supplied from the buffer tank to clean and pressurize each adsorption tower.

水電解装置４は、水電解により高純度の水素及び酸素を発生し、上記改質器２及び水素精製器３に供給する。水電解装置４としては、例えばプロトン伝導高分子膜を用いた固体高分子水電解装置やアルカリ水電解装置等を用いることができる。   The water electrolysis apparatus 4 generates high-purity hydrogen and oxygen by water electrolysis and supplies the hydrogen and oxygen to the reformer 2 and the hydrogen purifier 3. As the water electrolysis device 4, for example, a solid polymer water electrolysis device using a proton conducting polymer membrane, an alkaline water electrolysis device, or the like can be used.

当該水素製造装置１が備える制御手段は、後述する水素製造装置の停止方法を実行する制御装置であり、具体的には、改質器２への原料ガスＡ及び水蒸気Ｂの供給を停止すると共に、水電解装置４で発生した高純度水素ガスＦにより改質器２内をパージするように制御する装置である。この制御装置としては公知のものを用いることができる。   The control means provided in the hydrogen production apparatus 1 is a control apparatus that executes a hydrogen production apparatus stop method, which will be described later. Specifically, the supply means A and the steam B are stopped from being supplied to the reformer 2. This is a device for controlling the interior of the reformer 2 to be purged with the high purity hydrogen gas F generated in the water electrolysis device 4. A known device can be used as this control device.

＜水素製造装置の停止方法＞
本発明の水素製造装置の停止方法は、図３に示すように改質器２への原料ガスＡ及び水蒸気Ｂの供給停止後に上記改質器２に水電解装置４で発生した高純度水素ガスＦを供給する手順で行われる。すなわち、まず改質器２への酸素ガスＧの供給を停止し、改質器２の加熱を停止する（手順Ｓ１０）。続いて、原料ガスＡの供給を停止し、改質器２内の改質反応を停止させる（手順Ｓ２０）。この時点では改質器２内へは水蒸気Ｂのみが供給され、改質器２内は徐々に水蒸気で置換される。次に、改質器２から排出されるオフガスにおける原料ガス濃度が十分低下した時点で、水蒸気Ｂの供給を停止し（手順Ｓ３０）、水電解装置４で発生した高純度水素ガスＦを改質器２内に供給開始する（手順Ｓ４０）。その後、水分凝縮を避けられる圧力までオフガスにおける水蒸気の分圧が低下した時点で、高純度水素ガスＦの供給を停止する（手順Ｓ５０）。 <Method for stopping hydrogen production equipment>
As shown in FIG. 3, the hydrogen production apparatus stopping method of the present invention is a high-purity hydrogen gas generated in the water electrolysis apparatus 4 in the reformer 2 after the supply of the raw material gas A and the water vapor B to the reformer 2 is stopped. It is performed in the procedure of supplying F. That is, first, supply of the oxygen gas G to the reformer 2 is stopped, and heating of the reformer 2 is stopped (procedure S10). Subsequently, the supply of the raw material gas A is stopped, and the reforming reaction in the reformer 2 is stopped (procedure S20). At this time, only the steam B is supplied into the reformer 2, and the interior of the reformer 2 is gradually replaced with steam. Next, when the concentration of the raw material gas in the off-gas discharged from the reformer 2 is sufficiently lowered, the supply of the steam B is stopped (step S30), and the high-purity hydrogen gas F generated in the water electrolysis apparatus 4 is reformed. Supply is started in the container 2 (step S40). After that, when the partial pressure of water vapor in the off gas is reduced to a pressure at which moisture condensation can be avoided, the supply of the high purity hydrogen gas F is stopped (procedure S50).

上記手順Ｓ３０において、水蒸気Ｂの供給を停止する際のオフガスにおける原料ガス濃度は、使用する触媒の種類、運転温度、改質器容量、蒸気流量等の条件に合わせて適宜設計される。水蒸気Ｂの供給を停止する際のオフガスにおける原料ガス濃度の上限としては、１０ｍｏｌ％が好ましく、１ｍｏｌ％がより好ましい。上記オフガスにおける原料ガス濃度が上記上限を超える場合、改質器２内の原料ガス濃度が高くなり高純度水素ガスＦでパージするまでの間に改質器２内に炭素が析出するおそれがある。   In the procedure S30, the raw material gas concentration in the off-gas when the supply of the water vapor B is stopped is appropriately designed according to conditions such as the type of catalyst used, the operating temperature, the reformer capacity, and the steam flow rate. The upper limit of the raw material gas concentration in the off gas when the supply of the water vapor B is stopped is preferably 10 mol%, and more preferably 1 mol%. When the raw material gas concentration in the off gas exceeds the upper limit, the raw material gas concentration in the reformer 2 becomes high and carbon may be deposited in the reformer 2 until the high purity hydrogen gas F is purged. .

また上記手順Ｓ５０において、高純度水素ガスＦの供給を停止する際のオフガスにおける水蒸気の分圧は、改質器２の停止後の温度（保温温度）に合わせて適宜設計される。高純度水素ガスＦの供給を停止する際のオフガスにおける水蒸気の分圧の上限としては、５０ｋＰａが好ましく、２ｋＰａがより好ましい。上記オフガスにおける水蒸気の分圧が上記上限を超える場合、水分凝縮が発生し、改質器２内の触媒が劣化するおそれがある。   Further, in the procedure S50, the partial pressure of water vapor in the off-gas when the supply of the high purity hydrogen gas F is stopped is appropriately designed according to the temperature after the reformer 2 is stopped (heat retention temperature). The upper limit of the partial pressure of water vapor in the off gas when the supply of the high purity hydrogen gas F is stopped is preferably 50 kPa, and more preferably 2 kPa. When the partial pressure of water vapor in the off-gas exceeds the upper limit, moisture condensation occurs and the catalyst in the reformer 2 may be deteriorated.

なお、上記水電解装置４から発生する高純度水素ガスＦは水電解装置４の耐圧以下の圧力を有するため、改質器２内の運転圧が水電解装置４の耐圧（例えば１ＭＰａ）以下であれば高純度水素ガスＦを圧送するポンプは不要とすることができる。   In addition, since the high purity hydrogen gas F generated from the water electrolysis apparatus 4 has a pressure not higher than the pressure resistance of the water electrolysis apparatus 4, the operating pressure in the reformer 2 is not higher than the pressure resistance (for example, 1 MPa) of the water electrolysis apparatus 4. If it exists, the pump which pumps the high purity hydrogen gas F can be made unnecessary.

＜その他の実施形態＞
本発明の水素製造装置の停止方法は、上記実施形態に限定されるものではない。上記水素製造装置の停止方法では改質器への原料ガス及び水蒸気の供給停止後に改質器に水電解装置で発生した高純度水素ガスを供給したが、本発明の水素製造装置の停止方法は、図４及び図５に示すように水蒸気の供給停止前に改質器に水電解装置で発生した高純度水素ガスを供給することも可能である。この場合、高純度水素ガスの供給開始は原料ガスの供給停止前後の任意のタイミングで行うことができ、水蒸気の供給停止タイミングは上記実施形態と同様に、オフガスにおける原料ガス濃度が一定値以下となった場合とすることができる。 <Other embodiments>
The method for stopping the hydrogen production apparatus of the present invention is not limited to the above embodiment. In the method for stopping the hydrogen production apparatus, the high purity hydrogen gas generated in the water electrolysis apparatus was supplied to the reformer after the supply of the raw material gas and steam to the reformer was stopped. As shown in FIGS. 4 and 5, it is also possible to supply high-purity hydrogen gas generated in the water electrolysis apparatus to the reformer before stopping the supply of water vapor. In this case, the supply of high-purity hydrogen gas can be started at an arbitrary timing before and after the supply of the raw material gas is stopped. It can be the case.

また、当該水素製造装置の停止方法で用いる水素製造装置は、上記実施形態のものに限定されず、例えば水素精製器が有する吸着塔の数は３に限定されず、２又は４以上であってもよい。但し、均圧操作によって効率よく吸着塔の再生及び昇圧を行うためには３以上の吸着塔を設けることが好ましい。   Further, the hydrogen production apparatus used in the method for stopping the hydrogen production apparatus is not limited to the one in the above embodiment. For example, the number of adsorption towers included in the hydrogen purifier is not limited to 3, and is 2 or 4 or more. Also good. However, it is preferable to provide three or more adsorption towers in order to efficiently regenerate and raise the pressure of the adsorption towers by pressure equalizing operation.

なお、水素精製器は２段以上に分かれていてもよく、例えば一酸化炭素を吸着する第一の吸着塔群と、一酸化炭素以外の不純物を吸着する第二の吸着塔群とを有し、改質ガスをこの第一の吸着塔群及び第二の吸着塔群に直列で供給することで不純物を除去する方法を採用することもできる。   The hydrogen purifier may be divided into two or more stages, and has, for example, a first adsorption tower group that adsorbs carbon monoxide and a second adsorption tower group that adsorbs impurities other than carbon monoxide. A method of removing impurities by supplying the reformed gas in series to the first adsorption tower group and the second adsorption tower group may be employed.

さらに、水素精製器の吸着塔の洗浄又は昇圧は、水電解装置から発生しる高純度水素ガス以外に、他の吸着塔から発生する水素ガスを用いて行うこともできる。   Furthermore, the washing or pressurization of the adsorption tower of the hydrogen purifier can be performed using hydrogen gas generated from another adsorption tower in addition to the high-purity hydrogen gas generated from the water electrolysis apparatus.

また、本発明の水素製造装置の停止方法及び水素製造装置は、自己熱型の改質器の代わりに酸化反応を利用せず外部加熱によって水蒸気改質を行う改質器を用いてもよい。   The hydrogen production apparatus stopping method and the hydrogen production apparatus of the present invention may use a reformer that performs steam reforming by external heating without using an oxidation reaction, instead of the self-heating type reformer.

さらに、当該水素製造装置の停止方法は上述の制御装置により自動化して行うことが好適であるが、手動で行ってもよい。   Furthermore, although it is preferable that the method for stopping the hydrogen production apparatus is automated by the above-described control apparatus, it may be performed manually.

以上説明したように、当該水素製造装置の停止方法は、改質器内の触媒の劣化を防止しつつ、装置が完全に停止するまでの時間を短縮化でき、かつ装置を小型化できるため、燃料電池等に水素を供給する水素製造装置に好適に用いることができる。また、当該水素製造装置は、このような水素製造装置として好適に用いることができる。   As described above, the method for stopping the hydrogen production apparatus can reduce the time until the apparatus completely stops while preventing deterioration of the catalyst in the reformer, and can reduce the size of the apparatus. It can be suitably used in a hydrogen production apparatus that supplies hydrogen to a fuel cell or the like. Moreover, the said hydrogen production apparatus can be used suitably as such a hydrogen production apparatus.

１ 水素製造装置
２ 改質器
３ 水素精製器
４ 水電解装置
５ａ，５ｂ，５ｃ 吸着塔
１０ 原料ガス供給ライン
１１ 水蒸気供給ライン
１２ 改質ガス供給ライン
１３ 改質ガス回収ライン
１４ 高純度水素ガス供給ライン
１５ 酸素ガス供給ライン
１０１ 改質ガス導入ライン
１０２ オフガス排出ライン
１０３ 水素ガス回収ライン
Ａ 原料ガス
Ｂ 水蒸気
Ｃ 改質ガス
Ｄ 水素ガス
Ｅ オフガス
Ｆ 高純度水素ガス
Ｇ 酸素ガス DESCRIPTION OF SYMBOLS 1 Hydrogen production apparatus 2 Reformer 3 Hydrogen purifier 4 Water electrolysis apparatus 5a, 5b, 5c Adsorption tower 10 Raw material gas supply line 11 Steam supply line 12 Reformed gas supply line 13 Reformed gas recovery line 14 High purity hydrogen gas supply Line 15 Oxygen gas supply line 101 Reformed gas introduction line 102 Off gas discharge line 103 Hydrogen gas recovery line A Raw material gas B Water vapor C Reformed gas D Hydrogen gas E Off gas F High purity hydrogen gas G Oxygen gas

Claims (4)

炭化水素含有原料ガスの水蒸気改質により水素及び一酸化炭素を含む改質ガスを生成する改質部と、この改質ガスのＣＯ変成により水素リッチな変成ガスを排出する変成部とを有する改質器を備える水素製造装置の停止方法であって、
上記水素製造装置が水電解装置をさらに備え、
上記改質器への原料ガス及び水蒸気の供給を停止すると共に、上記水電解装置で発生した水素ガスにより上記改質器内をパージすることを特徴とする水素製造装置の停止方法。 A reforming section that generates reformed gas containing hydrogen and carbon monoxide by steam reforming of the hydrocarbon-containing source gas, and a reforming section that discharges hydrogen-rich modified gas by CO conversion of the reformed gas. A method for stopping a hydrogen production apparatus including a quality device,
The hydrogen production apparatus further comprises a water electrolysis device,
A method for stopping a hydrogen production apparatus, wherein the supply of raw material gas and water vapor to the reformer is stopped, and the interior of the reformer is purged with hydrogen gas generated in the water electrolysis apparatus. 炭化水素含有原料ガスの水蒸気改質により水素及び一酸化炭素を含む改質ガスを生成する改質部と、この改質ガスのＣＯ変成により水素リッチな変成ガスを排出する変成部とを有する改質器を備える水素製造装置であって、
水電解装置と、
上記改質器への原料ガス及び水蒸気の供給を停止すると共に、上記水電解装置で発生した水素ガスにより上記改質器内をパージする制御手段と
をさらに備えることを特徴とする水素製造装置。 A reforming section that generates reformed gas containing hydrogen and carbon monoxide by steam reforming of the hydrocarbon-containing source gas, and a reforming section that discharges hydrogen-rich modified gas by CO conversion of the reformed gas. A hydrogen production apparatus comprising a quality device,
A water electrolysis device,
And a control means for stopping supply of the raw material gas and water vapor to the reformer and purging the interior of the reformer with hydrogen gas generated by the water electrolysis apparatus. 上記改質器が酸素含有ガスの酸化により改質反応に必要な熱を得る自己熱型の改質器であり、
上記酸素含有ガスとして上記水電解装置で発生した酸素ガスを改質器に供給する請求項２に記載の水素製造装置。 The above reformer is a self-heating type reformer that obtains heat necessary for the reforming reaction by oxidizing the oxygen-containing gas,
The hydrogen production apparatus according to claim 2, wherein oxygen gas generated in the water electrolysis apparatus is supplied to the reformer as the oxygen-containing gas. 上記変成ガス中の水素以外のガスをＰＳＡ方式によって吸着する吸着塔を有する水素精製器をさらに備え、
上記吸着塔の洗浄及び／又は昇圧に上記水電解装置で発生した水素ガスを用いる請求項２又は請求項３に記載の水素製造装置。 A hydrogen purifier having an adsorption tower for adsorbing a gas other than hydrogen in the metamorphic gas by the PSA method;
The hydrogen production apparatus according to claim 2 or 3, wherein hydrogen gas generated in the water electrolysis apparatus is used for cleaning and / or increasing the pressure of the adsorption tower.
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