JPH03218903A - Hydrogen refiner - Google Patents
Hydrogen refinerInfo
- Publication number
- JPH03218903A JPH03218903A JP2011828A JP1182890A JPH03218903A JP H03218903 A JPH03218903 A JP H03218903A JP 2011828 A JP2011828 A JP 2011828A JP 1182890 A JP1182890 A JP 1182890A JP H03218903 A JPH03218903 A JP H03218903A
- Authority
- JP
- Japan
- Prior art keywords
- reformed gas
- hydrogen
- combustion
- raw material
- fuel cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000007789 gas Substances 0.000 claims abstract description 96
- 238000011084 recovery Methods 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 238000006057 reforming reaction Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 238000002407 reforming Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000000446 fuel Substances 0.000 description 51
- 210000004027 cell Anatomy 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000012528 membrane Substances 0.000 description 9
- 239000005518 polymer electrolyte Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010248 power generation Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000000567 combustion gas Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 210000005056 cell body Anatomy 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明は、水素原料の加熱に伴う改質反応により生成す
る改質ガスか゜ら一酸化炭素を取り除く水素精製装置に
関し、特に比較的低温で作動する固体高分子電解質膜燃
料電池を用いた発電システムに応用して好適なものであ
る。[Detailed description of the invention] Industrial application field> The present invention relates to a hydrogen purification device that removes carbon monoxide from reformed gas produced by a reforming reaction accompanying heating of a hydrogen raw material, and particularly relates to a hydrogen purification device that removes carbon monoxide from a reformed gas produced by a reforming reaction accompanying heating of a hydrogen raw material. It is suitable for application to a power generation system using an operating solid polymer electrolyte membrane fuel cell.
く従来の技術〉
金属等の還元ガスとして有効な水素は、燃料電池用の反
応ガスとしても利用できることは周知の通りである。こ
の燃料電池は、資源の枯渇問題を有する化石燃料を使う
必要がない上、騒音をほとんど発生せず、エネルギの回
収効率も他のエネルギ機関と較べて非常に高くできる等
の優れた特徴を持っているため、例えばビルディング単
位や工場単位の比較的小型の発電プラントとして利用さ
れている。BACKGROUND ART It is well known that hydrogen, which is effective as a reducing gas for metals, can also be used as a reaction gas for fuel cells. This fuel cell does not require the use of fossil fuels, which have resource depletion issues, generates almost no noise, and has excellent features such as being able to recover energy much more efficiently than other energy engines. Therefore, it is used as a relatively small power generation plant for each building or factory, for example.
近年、この燃料電池を車載用の内燃機関に代えて作動す
るモータの電源として利用し、このモータにより車両等
を駆動することが考えられている。この場合に重要なこ
とは、反応によって生成する物質等をできるだけ再利用
することは当然のこととして、車載用であることからも
明らかなように、余り大きな出力は必要でないものの、
全ての付帯設備と共に可能な限り小型であることが望ま
しく、このような点から固体高分子電解質膜燃料電池が
注目されている。In recent years, it has been considered to use this fuel cell as a power source for a motor that operates in place of an internal combustion engine in a vehicle, and to use this motor to drive a vehicle or the like. What is important in this case is that it is natural to reuse the substances produced by the reaction as much as possible, and although it is clear from the fact that it is for automotive use that a large output is not required.
It is desirable that the fuel cell be as small as possible, along with all incidental equipment, and from this point of view, solid polymer electrolyte membrane fuel cells are attracting attention.
かかる固体高分子電解質膜燃料電池は、固体高分子電解
質膜の両側に触媒を含むガス拡散電極を接合したもので
あり、メタノールと水等で構成される水素原料を改質し
て得られる改質ガスを反応ガスとしてガス拡散電極の陽
極（以下、これを水素極と呼称する）側に供給して発電
する形式が取られる。Such a solid polymer electrolyte membrane fuel cell is a solid polymer electrolyte membrane in which gas diffusion electrodes containing a catalyst are bonded to both sides of the solid polymer electrolyte membrane. A method is adopted in which a gas is supplied as a reaction gas to the anode (hereinafter referred to as a hydrogen electrode) side of a gas diffusion electrode to generate electricity.
ここで問題となるのは、ガス拡散電極に含まれる反応触
媒が一酸化炭素（以下、ＣＯと記述する）によって被毒
し、発電効率が低下し易くなることである。特に、１０
０゜Ｃ前後の低温で作動する燃料電池の場合にはこの傾
向が極端となり、最悪の場合には運転不可能？状態とな
ることが知られている。このため、改質ガスを燃料電池
の水素極側に供給する際には、この改質ガス中のＣＯ濃
度を少なくする必要がある。特に、先に述べた低温で作
動する燃料電池の場合には、これを１０ｐｐｍ以下に抑
えなければならない。The problem here is that the reaction catalyst contained in the gas diffusion electrode is poisoned by carbon monoxide (hereinafter referred to as CO), which tends to reduce power generation efficiency. In particular, 10
In the case of fuel cells that operate at low temperatures around 0°C, this tendency becomes extreme, and in the worst case, it becomes impossible to operate. It is known that the condition Therefore, when supplying the reformed gas to the hydrogen electrode side of the fuel cell, it is necessary to reduce the CO concentration in the reformed gas. In particular, in the case of a fuel cell that operates at low temperatures as mentioned above, this must be kept below 10 ppm.
従来、固体高分子電解質膜燃料電池を使用する場合には
、改質ガスに水蒸気を添加して改質ガス中に含まれるＣ
Ｏを吸着除去するＣＯシフト触媒と接触させ、このＣＯ
を二酸化炭素（以下、ＣＯ■と記述する）に転化するＣ
Ｏシフト処理がなされている。つまり、このＣＯシフト
処理では
ＣＯ＋Ｈ２０→ＣＯ■＋Ｈ２
なる可逆反応が起こる。この際、反応温度が低いほど、
反応圧力が高いほど、水蒸気ゐ割合が高いほどそれぞれ
残留ＣＯ濃度を低下させることができる。例えば、鉄−
クロム系ＣＯシフト触媒を用い、反応温度を２００゜Ｃ
、反応圧力を２０ａｔｍ，ＣＯ中の炭素成分に対？る水
の割合を４としてＣＯシフト処理した場合、残留ＣＯ濃
度子約０．１％（１ ０ ０ ０ｐｐｍ）にまで下げる
ことが可能である。しかし、この燃料電池を用いた発電
システムを車載用にまとめることを前提とすると、種々
の制約が発生してくるため、現実的にはＣＯシフト処理
による残留ＣＯ濃度は、１％前後が限界である。Conventionally, when using a solid polymer electrolyte membrane fuel cell, water vapor is added to the reformed gas to remove carbon contained in the reformed gas.
This CO is brought into contact with a CO shift catalyst that adsorbs and removes O.
C that converts into carbon dioxide (hereinafter referred to as CO■)
O shift processing is being performed. That is, in this CO shift process, a reversible reaction occurs: CO+H20→CO2+H2. At this time, the lower the reaction temperature, the
The higher the reaction pressure and the higher the water vapor ratio, the lower the residual CO concentration can be. For example, iron-
Using a chromium-based CO shift catalyst, the reaction temperature was set at 200°C.
, the reaction pressure is 20 atm, relative to the carbon component in CO? If the CO shift treatment is carried out with the proportion of water being 4, it is possible to reduce the residual CO concentration to about 0.1% (1000 ppm). However, assuming that a power generation system using this fuel cell is to be installed on a vehicle, various restrictions will occur, so in reality, the residual CO concentration due to CO shift processing is limited to around 1%. be.
このため、１００゜Ｃ前後の低温で作動する固体高分子
電解質膜燃料電池に対して改質ガスを供給する場合には
、ＣＯシフト処理に加えて更にＣＯの除去を行う必要が
あり、例えば改質ガス中のＣＯを選択的に酸化させるい
わゆるセレクトオキソ反応と呼称される化学反応を利用
した方法が提案されている。つまり、このセレクトオキ
ソ反応ではセレクトオキソ触媒と接触状態にある改質ガ
ス中に空気或いは酸素を吹き込み、セレクトオキソ触媒
を利用して水素を酸化させることなく、この水素よりも
化学的に不安定なＣＯをＣＯ■に？化させるのである。Therefore, when supplying reformed gas to a solid polymer electrolyte membrane fuel cell that operates at a low temperature of around 100°C, it is necessary to remove CO in addition to the CO shift process. A method has been proposed that utilizes a chemical reaction called the so-called select oxo reaction, which selectively oxidizes CO in a quality gas. In other words, in this select oxo reaction, air or oxygen is blown into the reformed gas that is in contact with the select oxo catalyst, and the select oxo catalyst is used to generate hydrogen, which is chemically more unstable than hydrogen, without oxidizing it. CO to CO■? It is to make it become.
く発明が解決しようとする課題〉
セレクトオキソ反応によって改質ガス中の水素を余り酸
化させることなく、選択的にｃｏをＣＯ■に酸化させよ
うとした場合、改質ガスの反応温度を７０゜Ｃ程度に設
定することが最も効率良く反応を進めることができる。Problems to be Solved by the Invention When attempting to selectively oxidize CO to CO without significantly oxidizing hydrogen in the reformed gas by the select oxo reaction, the reaction temperature of the reformed gas should be set at 70°. Setting the temperature to about C allows the reaction to proceed most efficiently.
ところが、ＣＯシフト処理後の改質ガスの温度は２００
゜Ｃ前後の高温のため、この改質ガスがセレクトオキソ
反応の際に当該改質ガス中の水素の一部も酸化されてし
まい、燃料電池に供給すべき水素の絶対量が少な《なる
欠点を有する。However, the temperature of the reformed gas after the CO shift treatment is 200℃.
Due to the high temperature of around °C, part of the hydrogen in the reformed gas is oxidized when the reformed gas undergoes the select oxo reaction, resulting in a small absolute amount of hydrogen to be supplied to the fuel cell. has.
特に、燃料電池の水素極の被毒をほぼ完全に避ける目的
で残留ＣＯ濃度をＩＯｐｐｍ程度にまで低下させようと
すると、改質ガス中の水素の相当量が酸化されてしまい
、燃料電池の運転を継続することができなくなる不具合
が発生する。このため、実際には残留しＣＯ濃度を１０
０ｐｐｍ程度にまでしか下げることができなかった。In particular, if an attempt is made to reduce the residual CO concentration to about IOppm with the aim of almost completely avoiding poisoning of the hydrogen electrode of the fuel cell, a considerable amount of hydrogen in the reformed gas will be oxidized and the fuel cell will not be able to operate. A problem occurs that makes it impossible to continue. Therefore, it actually remains and reduces the CO concentration by 10
It was possible to lower it only to about 0 ppm.
く問題点を解決するための手段〉
本発明による水素精製装置は、水素原料を加熱してこの
加熱に伴う改質反応により前記水素原料から水素ガスを
含む改質ガスを生成させる改質装置と、この改質装置で
生成した改質ガス中のＣＯを選択的に吸着除去するＣＯ
低減装置と、このＣＯ低減装置からの改質ガスに含まれ
る微量のＣＯを更に酸化除去するＣＯ除去装置とを具え
た水素精製装置において、前記ＣＯ低減装置と前記ＣＯ
除去装置との間の改質ガス通路の途中にこれらＣＯ低減
装置からＣＯ除去装置へと流れる前記改質ガスにより回
転する排気タービンを有するエネルギ回収装置を設けた
ことを特徴とするものである。Means for Solving Problems> The hydrogen purification apparatus according to the present invention is a reformer that heats a hydrogen raw material and generates a reformed gas containing hydrogen gas from the hydrogen raw material through a reforming reaction accompanying the heating. , CO that selectively adsorbs and removes CO in the reformed gas generated by this reformer.
A hydrogen purification device comprising a CO reduction device and a CO removal device that further oxidizes and removes trace amounts of CO contained in the reformed gas from the CO reduction device, wherein the CO reduction device and the CO
The present invention is characterized in that an energy recovery device having an exhaust turbine rotated by the reformed gas flowing from the CO reduction device to the CO removal device is provided in the middle of the reformed gas passage between the CO reduction device and the CO removal device.
〈作用〉
改質装置にて生成した改質ガスがＣＯ低減装置に送られ
て来ると、このＣＯ低減装置のＣＯシフト触媒によって
改質ガス中の残留Ｃ０濃度が例えば１％程度にまで低下
する。この改質ガスの温度は２００℃程度であり、これ
が改質ガス通路を通ってＣＯ除去装置へと送られる。こ
の時、ＣＯ除去装置へと流れる改質ガスの主としてエン
タルピーにより排気タービンが駆動され、改質ガスが保
有するエネルギをエネルギ回収装置によって回収する。<Operation> When the reformed gas generated in the reformer is sent to the CO reduction device, the residual CO concentration in the reformed gas is reduced to, for example, about 1% by the CO shift catalyst of this CO reduction device. . The temperature of this reformed gas is about 200° C., and it is sent to the CO removal device through the reformed gas passage. At this time, the exhaust turbine is driven mainly by the enthalpy of the reformed gas flowing to the CO removal device, and the energy held by the reformed gas is recovered by the energy recovery device.
この結果、改質ガスは断熱膨張を起こしてその温度が例
えば７０゜Ｃ程度にまで低下し、ＣＯ除去装置のセレク
トオキソ反応により、改質ガス中の残留ＣＯ濃度が例え
ば１０ｐｐｍ程度にまで低下する。As a result, the reformed gas undergoes adiabatic expansion and its temperature drops to, for example, about 70°C, and due to the select oxo reaction of the CO removal device, the residual CO concentration in the reformed gas decreases to, for example, about 10 ppm. .
この時、ＣＯ除去装置に送り込まれる改質ガスは、エネ
ルギ回収装置の作用によってその温度が充分低下してお
り、この改質ガス中に含まれる水素の酸化反応はほとん
ど起こらず、水素の消費が抑制される。At this time, the temperature of the reformed gas sent to the CO removal device has been sufficiently lowered by the action of the energy recovery device, and almost no oxidation reaction of hydrogen contained in this reformed gas occurs, reducing hydrogen consumption. suppressed.
〈実施例〉
本発明による水素精製装置を固体高分子電解質膜燃料電
池（以下、単に燃料電池と呼称する）を用いた発電シス
テムに応用したー実施例の概念を表す第１図及びそのメ
タノール改質装置の部分の断面構造を表す第２図に示す
ように、改質装置１１の筒状をなす燃焼筒１２の一端側
には、後述する空気とメタノール１３とからなる始動用
の燃焼ガス或いは空気と燃料電池本体１４からの未反応
ガスとからなる定常運転時の燃焼ガスを燃焼させるため
の燃焼室１５が形成されており、４００゜Ｃ〜１２００
℃程度の温度に設定されるこの燃焼室１５内には、燃焼
ガスの燃焼を促進させるための燃焼触媒ｌ６が保持され
ている。<Example> The hydrogen purification apparatus according to the present invention is applied to a power generation system using a solid polymer electrolyte membrane fuel cell (hereinafter simply referred to as a fuel cell). As shown in FIG. 2, which shows the cross-sectional structure of the reformer, one end of the cylindrical combustion tube 12 of the reformer 11 is filled with starting combustion gas consisting of air and methanol 13, which will be described later. A combustion chamber 15 is formed to combust combustion gas during steady operation consisting of air and unreacted gas from the fuel cell main body 14, and has a temperature of 400°C to 1200°C.
A combustion catalyst 16 for promoting combustion of combustion gas is held in the combustion chamber 15, which is set at a temperature of approximately .degree.
なお、この燃焼触媒１６としては、例えばプラチナ（Ｐ
ｔ）及びパラジウム（Ｐｄ）の内の少なくとも一つの元
素を含むもの、或いは鉄（Ｆｅ）及びコバルト（Ｃ ｏ
）及びニッケル（Ｎｉ）及びマンガン（Ｍｎ）及び銅（
Ｃｕ）の内の少なくとも一つの元素を含むものを挙げる
ことができ、本実施例では直径が４ｍｍ〜６ｍｍの球状
のものを燃焼室１５内に充填している。Note that this combustion catalyst 16 is made of platinum (P), for example.
t) and palladium (Pd), or iron (Fe) and cobalt (Co
) and nickel (Ni) and manganese (Mn) and copper (
In this embodiment, the combustion chamber 15 is filled with spherical particles having a diameter of 4 mm to 6 mm.
先端側が燃焼室１５に臨む燃焼ノズル１７を中央部に貫
通状態で固定した端板１８は、この燃焼筒１２の一端に
接合されており、前記燃焼ノズルｌ７の先端部には逆火
防止機能を有する燃料分散器１９が装着されている。An end plate 18, in which a combustion nozzle 17 whose tip side faces the combustion chamber 15 is fixed in a penetrating state in the center thereof, is joined to one end of this combustion tube 12, and the tip of the combustion nozzle l7 is provided with a flashback prevention function. A fuel distributor 19 is installed.
そして、この燃料分散器１９から燃焼室１５内に供給さ
れる燃焼ガスは、燃焼触媒１６により着火燃焼して４０
０゜Ｃ〜１２ｏＯ℃程度の温度となる。又、この燃焼ノ
ズル１７には燃料供給管２０を介してメタノールタンク
２１が連結されている。そして、この燃料供給管２０の
途中には、燃料電池の始動時に前記メタノールタンク２
１内のメタノール１３を燃焼ノズルｌ７側へ圧送する図
示しない始動用燃料供給ポンプと、この始動用燃料供給
ポンプから供給されるメタノール１３を蒸発気化させて
燃焼ノズル１７へ送り込むための図示しないメタノール
気化器とを具えた始動装置２２が設けられている。The combustion gas supplied from this fuel distributor 19 into the combustion chamber 15 is ignited and combusted by the combustion catalyst 16, resulting in 40%
The temperature will be about 0°C to 12oO°C. Further, a methanol tank 21 is connected to this combustion nozzle 17 via a fuel supply pipe 20. The methanol tank 2 is placed in the middle of this fuel supply pipe 20 when starting up the fuel cell.
A starting fuel supply pump (not shown) that pressure-feeds methanol 13 in 1 to the combustion nozzle 17 side, and a methanol vaporizer (not shown) that evaporates and vaporizes the methanol 13 supplied from this starting fuel supply pump and sends it to the combustion nozzle 17. A starting device 22 is provided with a device.
この始動装置２゛２と燃焼ノズル１７との間の燃料供給
管２０の途中には、一端側が空気を燃焼室ｌ５側に送り
込むだめのブロワ２３に接続する燃焼用空気供給管２４
の他端部が連結されている。前記ブロワ２３には、電源
である蓄電池２５から電気を供給されるブロワ駆動モー
タ２６が連結され、このブロワ駆動モータ２６を作動さ
せることによって、燃焼用の空気が前記燃焼ガスの一部
として燃焼用空気供給管２４から燃料供給管２０及び燃
焼ノズル１７を介し燃焼室１５に送り込まれるようにな
っている。In the middle of the fuel supply pipe 20 between the starter 2'2 and the combustion nozzle 17, there is a combustion air supply pipe 24 whose one end is connected to a blower 23 for feeding air into the combustion chamber 15.
The other end is connected. A blower drive motor 26 that is supplied with electricity from a storage battery 25 as a power source is connected to the blower 23, and by operating the blower drive motor 26, combustion air is converted into combustion air as part of the combustion gas. The air is fed from the air supply pipe 24 to the combustion chamber 15 via the fuel supply pipe 20 and the combustion nozzle 17.
ＳＵＳ３１０Ｓ材等のステンレス鋼で形成される前記燃
焼筒１２の内周面には、耐熱れんが等で構成した断熱層
２７が形成されて燃焼室１５内を保温し、燃焼筒１２の
外周面からの熱放散を防止している。これにより、燃焼
室１５内が充分高温となった場合には、燃焼触媒ｌ６の
作用と相俟って後述する燃料電池本体１４からの未反応
ガスと空気とを供給するだけで燃焼室１５内を充分高温
に保つことができるので、始動装置２２・゛の運転を停
止し、メタノールｌ３の供給は行わないようになってい
る。A heat insulating layer 27 made of heat-resistant brick or the like is formed on the inner circumferential surface of the combustion tube 12 made of stainless steel such as SUS310S material to keep the inside of the combustion chamber 15 warm and to prevent heat from the outer circumferential surface of the combustion tube 12. Prevents heat dissipation. As a result, when the inside of the combustion chamber 15 reaches a sufficiently high temperature, the inside of the combustion chamber 15 can be heated by simply supplying unreacted gas and air from the fuel cell main body 14, which will be described later, together with the action of the combustion catalyst l6. can be kept at a sufficiently high temperature, the operation of the starter device 22.' is stopped and methanol 13 is not supplied.
前記燃焼筒１２の周囲には、熱交換笥２８がこの燃焼筒
１２の外周面と隙間を隔てて同心状に配置されている。A heat exchange tray 28 is disposed concentrically around the combustion tube 12 with a gap spaced from the outer peripheral surface of the combustion tube 12.
これら燃焼筒１２と熱交換筒２８との隙間の他端側は、
燃焼筒１２の他端部に刻設した切欠通路２９を介して燃
焼室１５内に連通し、この隙間の一端側には燃焼室１５
内で燃焼した燃焼排ガスを外部に導く排気管３０が接続
している。The other end of the gap between the combustion tube 12 and the heat exchange tube 28 is
The combustion chamber 15 is communicated with the combustion chamber 15 through a notch passage 29 carved in the other end of the combustion tube 12, and the combustion chamber 15 is connected to one end of this gap.
An exhaust pipe 30 is connected to guide the combustion exhaust gas burned inside to the outside.
前記燃焼笥１２と熱交換筒２８との隙間には、改質原料
予熱管３１が螺旋状に配管されている。そして、この改
質原料予熱管３１の一端側か熱交換筒２８を貫通し、水
素原料供給管３２を介して前記メタノールタンク２１に
接続する一方、当該改質原料予熱管３１の他端側が燃焼
室ｌ５の内周面に沿って螺旋状に配管された改質原料加
熱管３３の一端側に連結されている。前記改質装置１１
とメタノールタンク２１との間の水素原料供給・管３２
の途中には、原料ポンプ駆動モータ３４の作動により、
メタノールタンク２１内のメタノール１３を改質装置ｌ
ｌ側へ圧送する原料供給ボンブ３５が取り付けられてい
る。更に、この水素原料供給管３２の途中には、一端側
が水タンク３６に連通ずる水供給管３７の他端側か接続
しており、この水供給管３７の途中には、前記メタノー
ル１３と共に水素原料を構成する水タンク３６内の水３
８を水ボンブ駆動モータ３９の作動により、水素原料供
給管３２内に圧送するための水供給ボンブ４０が取り付
けられている。A reforming material preheating pipe 31 is spirally arranged in the gap between the combustion stove 12 and the heat exchange cylinder 28 . One end of this reforming material preheating pipe 31 passes through the heat exchange cylinder 28 and is connected to the methanol tank 21 via the hydrogen material supply pipe 32, while the other end of the reforming material preheating pipe 31 is combusted. It is connected to one end side of a reforming material heating pipe 33 that is spirally piped along the inner peripheral surface of the chamber l5. The reformer 11
Hydrogen raw material supply/pipe 32 between the and methanol tank 21
During the process, due to the operation of the raw material pump drive motor 34,
The methanol 13 in the methanol tank 21 is converted into a reformer l.
A raw material supply bomb 35 is attached to feed the raw material under pressure to the l side. Furthermore, one end of this hydrogen raw material supply pipe 32 is connected to the other end of a water supply pipe 37 whose one end communicates with a water tank 36 , and the hydrogen raw material supply pipe 32 is connected to the other end of a water supply pipe 37 which communicates with a water tank 36 . Water 3 in the water tank 36 constituting the raw material
A water supply bomb 40 is attached to feed the hydrogen gas into the hydrogen raw material supply pipe 32 by the operation of a water bomb drive motor 39.
従って、メタノールｌ３と水３８とからなる改質原料が
改質原料予熱管３１を通って水素原料加熱管３３へと移
動する間に、燃焼室ｌ５から燃焼筒１２と熱交換笥２８
との隙間を通って排気管３０へ向けて流れる高温の燃焼
排ガスとの間で熱交換が行われ、水素原料は２００゜Ｃ
〜５００゜Ｃ程度にまで予熱されるようになっている。Therefore, while the reformed raw material consisting of methanol l3 and water 38 passes through the reformed raw material preheating pipe 31 and moves to the hydrogen raw material heating pipe 33, from the combustion chamber l5 to the combustion tube 12 and the heat exchange column 28.
Heat exchange is performed between the hydrogen raw material and the high-temperature combustion exhaust gas flowing toward the exhaust pipe 30 through the gap between the
It is designed to be preheated to about ~500°C.
この場合、メタノール１３と水３８との混合比は、１モ
ルのメタノールに対して水を０．０５モルから５モル程
度に設定することが望ましく、更に燃焼排ガスを完全燃
焼させるために燃焼筒１２と熱交換笥２８との隙間に前
述した燃焼触媒１６を充填することも有効である。本実
施例では、直径が１ｍｍ〜３ｍｍの球状をなす前述した
燃焼触媒ｌ６をこれら燃焼筒ｌ２と熱交換筒２５との隙
間に充填している。In this case, it is desirable to set the mixing ratio of methanol 13 and water 38 to approximately 0.05 to 5 moles of water per 1 mole of methanol. It is also effective to fill the gap between the combustion catalyst 16 and the heat exchange tray 28 with the combustion catalyst 16 described above. In this embodiment, the above-described combustion catalyst l6 having a spherical shape with a diameter of 1 mm to 3 mm is filled in the gap between the combustion cylinder l2 and the heat exchange cylinder 25.
なお、前記原料ポンプ駆動モータ３４や水ポンプ駆動モ
ータ３９は、蓄電池２５から供給される電気によって運
転されるようになっている。The raw material pump drive motor 34 and the water pump drive motor 39 are operated by electricity supplied from the storage battery 25.
前記燃焼笥１２の中央部には、改質原料加熱管３３の他
端側に接続する改質用ヘツダ４１が設けられており、こ
の改質用ヘツダ４１には燃焼筒１２の他端側に延びる相
互に平行な複数本の改質ガス生成管４２の一端側が整流
？オリフィス４３を介してそれぞれ連結されている。こ
・れら改質ガス生成管４２の他端側には、多数の連通口
４４を有するパンチングメタルで形成した一枚の封板４
５が接合されており、当該改質ガス生成管４２の内部に
は水素原料加熱管３３で加熱された水素原料の改質反応
を促進するための改質用触媒４６がそれぞれ充填されて
いる。メタノール１３と水３８とが混合した水素原料は
この改質ガス生成管４２内で
ＣＨ３０Ｈ＋ｎＨ２０ −” （１−ｎ）ＣＯ＋ｎ
ＣＯ■＋（２＋ｎ）Ｈ２但し、０＜ｎ＜１
なる改質反応を起こし、上記化学式の右辺に示される改
質ガスを生成する。この場合、原料ガスの改質反応を効
率良《行わせるためには、改質ガス生成管４２内の圧力
を一平方センチメートル当たり３ ｋｇ重〜２０ｋｇ重
程度に設定し、又、この改質ガス生成管４２内の温度を
２００゜Ｃ〜６００゜Ｃ程度に設定することが望ましい
。A reforming header 41 connected to the other end of the reforming material heating pipe 33 is provided in the center of the combustion chamber 12. Is one end side of the plurality of mutually extending reformed gas generation pipes 42 rectified? They are connected to each other via an orifice 43. On the other end side of these reformed gas generation tubes 42, there is a sealing plate 4 made of punched metal having a large number of communication ports 44.
5 are connected to each other, and a reforming catalyst 46 for promoting the reforming reaction of the hydrogen raw material heated by the hydrogen raw material heating tube 33 is filled inside each of the reformed gas generation pipes 42 . The hydrogen raw material in which methanol 13 and water 38 are mixed is CH30H+nH20 −” (1-n)CO+n in this reformed gas generation pipe 42.
CO■+(2+n)H2 However, a reforming reaction occurs where 0<n<1, and the reformed gas shown on the right side of the above chemical formula is produced. In this case, in order to carry out the reforming reaction of the raw material gas efficiently, the pressure inside the reformed gas generation pipe 42 is set to about 3 kg to 20 kg per square centimeter, and the reformed gas generated It is desirable to set the temperature inside the tube 42 to about 200°C to 600°C.
なお、この改質用触媒４６としては、例えばプラチナ（
Ｐｔ）及．びパラジウム（Ｐｄ）及びロジウム（Ｒｈ）
及びニッケル（Ｎｉ）の内の少な《とも一つの元素を含
むもの、或いは銅（Ｃｕ）及び亜鉛（Ｚｎ）及びクロム
（Ｃｒ）の内の少なくとも一つの元素を含むものを挙げ
ることができ、本実施例では直径が３ｍｍで長さが３
ｍｍの円笥状のものを改質ガス生成管４２の内部に充填
している。Note that this reforming catalyst 46 may be made of, for example, platinum (
Pt) and. and palladium (Pd) and rhodium (Rh)
and nickel (Ni), or copper (Cu), zinc (Zn), and chromium (Cr); In the example, the diameter is 3 mm and the length is 3 mm.
The inside of the reformed gas generation pipe 42 is filled with a round cup-shaped material having a diameter of mm.
ところで、本発明では燃焼筒１２内の改質ガス生成管４
２の周囲に燃焼触媒１６を充填しているため、この改質
ガス生成管４２の周囲を流れる燃焼排ガスの流速が高め
られる結果、改質ガス生成管３９内での改質原料の改質
反応に必要な熱を効率良く供給することが可能である。By the way, in the present invention, the reformed gas generation pipe 4 in the combustion tube 12
Since the combustion catalyst 16 is filled around the reformed gas generating pipe 2, the flow rate of the combustion exhaust gas flowing around the reformed gas generating pipe 42 is increased, resulting in a reforming reaction of the reformed raw material in the reformed gas generating pipe 39. It is possible to efficiently supply the heat required for
一方、この改質装置１１の他端側には、ＣＯ低減装置４
７が封板４５に隣接状態で取り付けられており、改質ガ
ス生成管４２゛とこのＣＯ低減装置４７とは、封板４５
の連通口４４を介して連通している。そして、ＣＯ低減
装置４７には改質ガス生成管４・２内での水素原料の改
質反応により生成する改質ガス中のＣＯを低減させるＣ
Ｏシフト触媒４８が充填されているが、この改質ガスか
らＣＯを除去するのは、周知のように燃料電池本体１４
の水素極４９がＣＯによって被毒してしまい、電池とし
ての能力が極端に低下するのを防止するためである。On the other hand, on the other end side of this reformer 11, a CO reduction device 4 is provided.
7 is attached adjacent to the sealing plate 45, and the reformed gas generation pipe 42' and this CO reduction device 47 are connected to the sealing plate 45.
The communication ports 44 communicate with each other. The CO reduction device 47 is equipped with a carbon dioxide gas that reduces CO in the reformed gas generated by the reforming reaction of the hydrogen raw material in the reformed gas generation pipes 4 and 2.
Although the O shift catalyst 48 is filled, as is well known, the fuel cell main body 14 is responsible for removing CO from the reformed gas.
This is to prevent the hydrogen electrode 49 from being poisoned by CO and the performance of the battery to be extremely reduced.
なお、前記ＣＯシフト触媒４８としては、例えば銅（Ｃ
ｕ）及び亜鉛（Ｚｎ）の内の少なくとも一つの元素を含
むものを挙げることができるが、本実施例では直径が３
ｍｍで長さが３ｍｍの円筒状のものを採用している。In addition, as the CO shift catalyst 48, for example, copper (C
u) and zinc (Zn), but in this example, the diameter is 3.
A cylindrical piece with a length of 3 mm is used.
更に、前記ＣＯ低減装置４７に連通ずる改質ガス供給管
５０には、燃料電池本体１４の水素導入口５１が加湿装
置５２を介して接続し、改質ガス供給管５０内の改質ガ
スを適当な湿度に自動調整した状態で、燃料電池本体１
４の水素極４９側に送り込むようになっている。そして
、ＣＯ低減装置４７とこの加湿装置５２との間の改質ガ
ス供給管５０の途中には、前記蓄電池２５に接続する発
電機５３を連結した排気タービン５４と、改質ガス中の
ＣＯをセレクトオキソ反応によって除去する図示しない
セレクトオキソ触媒を充填したＣＯ除去装置５５とが、
改質装置１１側から順に設けられ、このＣＯ除去装置５
５によって精製された改質ガスが加湿装置５２により加
湿されて燃料電池本体１４の水素導入口５ｌへ送り込ま
れるようになっている。そして、この水素導入口５１か
ら燃料電池本体１４の水素極４９に送り込まれた改質ガ
スのうち、余剰の未反応ガスは燃料電池本体１４と前記
燃料供給管２０とを連通ずる燃焼用余剰ガス供給管５６
を介して燃焼ノズル１７に供給され、燃焼室１５内で燃
焼して水素原料加熱管３３内を流れる水素原料を加熱す
る。Further, a hydrogen inlet 51 of the fuel cell main body 14 is connected to the reformed gas supply pipe 50 communicating with the CO reduction device 47 via a humidifier 52, so that the reformed gas in the reformed gas supply pipe 50 is The fuel cell body 1 is placed in a state where the humidity is automatically adjusted to an appropriate level.
4 to the hydrogen electrode 49 side. In the middle of the reformed gas supply pipe 50 between the CO reduction device 47 and this humidifying device 52, there is an exhaust turbine 54 connected to a generator 53 connected to the storage battery 25, and an exhaust turbine 54 for reducing CO in the reformed gas. A CO removal device 55 filled with a select oxo catalyst (not shown) that removes CO by a select oxo reaction,
The CO removal device 5 is provided in order from the reformer 11 side.
The reformed gas purified by step 5 is humidified by a humidifier 52 and sent to the hydrogen inlet 5l of the fuel cell main body 14. Of the reformed gas sent from the hydrogen inlet 51 to the hydrogen electrode 49 of the fuel cell main body 14, surplus unreacted gas is used as surplus combustion gas that communicates the fuel cell main body 14 and the fuel supply pipe 20. Supply pipe 56
The hydrogen raw material is supplied to the combustion nozzle 17 through the combustion chamber 15 and burned in the combustion chamber 15 to heat the hydrogen raw material flowing through the hydrogen raw material heating pipe 33.
本実施例におけるエネルギ回収装置である排気タービン
５４を有する発電機５３は、Ｃ０低減装置４７からＣＯ
除去装置５５へ向けて改質ガス供給管５０内を流れる高
温の改質ガスにより、排気タービン５４を介して作動す
るものである。この時、排気タービン５４を通過してこ
れを駆動回転させる高温の改質ガスが断熱膨張するため
、その温度が急激に下降して低温となった改質ガスがＣ
Ｏ除去装置５５へ送られる。これにより、ＣＯ除去装置
５５でのセレクトオキソ反応が理想的に進み、水素の酸
化をほとんどさせることなく残留ＣＯ濃度を例えば１０
ｐｐｍ程度にまで低下させることができ、低温作動の燃
料電池であっても効率良《運転することが可能となる。A generator 53 having an exhaust turbine 54, which is an energy recovery device in this embodiment, collects CO from a CO reduction device 47.
It is operated by high-temperature reformed gas flowing through the reformed gas supply pipe 50 toward the removal device 55 via the exhaust turbine 54. At this time, the high-temperature reformed gas that passes through the exhaust turbine 54 and drives it to rotate expands adiabatically, so its temperature rapidly drops and the low-temperature reformed gas becomes carbon
It is sent to the O removal device 55. As a result, the select oxo reaction in the CO removal device 55 progresses ideally, and the residual CO concentration is reduced to, for example, 10% without oxidizing hydrogen.
It can be reduced to about ppm, making it possible to operate efficiently even in low-temperature operation fuel cells.
このような運転を実現するためには、先にも述べたよう
に改質ガス生成管４２内の改質ガスの圧力を一平方セン
チメートル当たり３ｋｇ重以上２０ｋｇ重程度までの範
囲に設定することが望ましい。又、本実施例では、エネ
ルギ回収装置として発電機５３を採用し、この発電機５
３により発電された電気を蓄電池２５に蓄え、ブロワ駆
動モータ２６や原料ポンプ駆動モーター３４，水ポンプ
駆動モータ３９等の電源として利用するようにしたが、
空気圧縮器等を排気タービン５４に連結し、これによっ
て得られる圧縮空気を燃焼室１５や燃料電池本体１４の
酸素極５７に供給するようにしても良い。In order to realize such an operation, as mentioned earlier, it is desirable to set the pressure of the reformed gas in the reformed gas generation pipe 42 to a range of 3 kg to 20 kg per square centimeter. . Further, in this embodiment, a generator 53 is employed as an energy recovery device, and this generator 5
The electricity generated by 3 is stored in the storage battery 25 and used as a power source for the blower drive motor 26, raw material pump drive motor 34, water pump drive motor 39, etc.
An air compressor or the like may be connected to the exhaust turbine 54, and compressed air obtained thereby may be supplied to the combustion chamber 15 or the oxygen electrode 57 of the fuel cell main body 14.
前記ブロワ２３と燃料電池本体１４に形成された空気導
入口５８とは、前記燃焼用空気供給管２４から分岐する
反応用空気供給管５９を介して連結され、前記ブロヮ駆
動モータ２６によって駆動されるブロワ２３からの加圧
空気が、この燃料電池本体１４の空気導入口５８に接続
する酸素極５７へ圧送されるようになっている。そして
、この空気導入口５８から燃料電池本体１４に送り込ま
れた空気は、この燃料電池本体１４内での反応生成水を
含んだ状態となって、燃料電池本体ｌ４の酸素極５７に
接続する気水分離器６Ωに供給され、この内の水分が水
回収管６１を介して水タンク３６に回収され、気体分が
排気管６２から外部に排出される。The blower 23 and an air inlet 58 formed in the fuel cell main body 14 are connected via a reaction air supply pipe 59 branching from the combustion air supply pipe 24, and are driven by the blower drive motor 26. Pressurized air from the blower 23 is forced to be sent to the oxygen electrode 57 connected to the air inlet 58 of the fuel cell main body 14. The air sent into the fuel cell main body 14 from this air inlet 58 contains water produced by the reaction within the fuel cell main body 14, and the air is connected to the oxygen electrode 57 of the fuel cell main body 14. The water is supplied to a water separator 6Ω, the water contained therein is collected into the water tank 36 via a water recovery pipe 61, and the gas component is discharged to the outside through an exhaust pipe 62.
一方、前記水タンク３６と燃料電池本体１４と加湿装置
５２とは、冷却用循環配管６３を介して連結されており
、これら水タンク３６と燃料電池本体１４との間の冷却
用循環配管６３の途中には、蓄電池２５から電気が供給
される循環ポンプ駆動モータ６４の作動により、水タン
ク３６内の水３８を燃料電池本体１４に供給してこの燃
料電池本体１４を冷却する循環ポンブ６５が設けられて
いる。前記加湿装置５２内には、燃料電池本体１４を冷
却した冷却水循環配管６３からの水３８と、改質ガス供
給管５０からの改質ガスとを仕切る図示しないガス拡散
膜が組み込まれており、この加湿装置５２内の水３８の
水蒸気分圧に対応した水蒸気が改質ガスに添加され、余
剰の水蒸気が冷却水循環配管６３から水タンク３６に戻
されるようになっている。On the other hand, the water tank 36, the fuel cell main body 14, and the humidifier 52 are connected via a cooling circulation pipe 63. A circulation pump 65 is provided in the middle, which cools the fuel cell body 14 by supplying water 38 in the water tank 36 to the fuel cell body 14 by operating a circulation pump drive motor 64 supplied with electricity from the storage battery 25. It is being A gas diffusion membrane (not shown) that partitions the water 38 from the cooling water circulation pipe 63 that cooled the fuel cell main body 14 and the reformed gas from the reformed gas supply pipe 50 is incorporated in the humidifying device 52. Water vapor corresponding to the water vapor partial pressure of the water 38 in the humidifier 52 is added to the reformed gas, and excess water vapor is returned to the water tank 36 from the cooling water circulation pipe 63.
このように、本実施例ではメタノールと水との混合物に
よる燃料電池を使用した発電システムとして本発明の水
素精製装置を応用したが、これ以外の例えば金属還元用
の水素製造装置等にも応用することができる。又、当然
のことであるが、本実施例以外の構造であっても水素精
製装置としてこの明細書の「特許請求の範囲」の欄に記
載した概念に含まれるものでありさえすれば、いがなる
構造のものを採用しても何ら問題は無い。As described above, in this example, the hydrogen purification device of the present invention was applied as a power generation system using a fuel cell using a mixture of methanol and water, but it can also be applied to other systems such as a hydrogen production device for metal reduction, etc. be able to. Also, as a matter of course, even structures other than those of this embodiment are acceptable as long as they are included in the concept described in the "Claims" column of this specification as a hydrogen purification device. There is no problem in adopting a structure in which
く発明の効果〉
本発明の水素精製装置によると、ＣＯ低減装置とＣＯ除
去装置との間にＣＯ低減装置からの改質ガスによって回
転する排気タービンを具えたエネルギ回収装置を組み込
んだので、ＣＯ低減装置からの高温の改質ガスがエネル
ギ回収装置を通過する間に断熱膨張し、低温となった改
質ガスがＣＯ除去装置に送られる。Effects of the Invention According to the hydrogen purification device of the present invention, an energy recovery device equipped with an exhaust turbine rotated by reformed gas from the CO reduction device is installed between the CO reduction device and the CO removal device, so that CO The hot reformed gas from the reduction device undergoes adiabatic expansion while passing through the energy recovery device, and the cooled reformed gas is sent to the CO removal device.
この結果、水素を酸化させることなくＣＯを選択的に酸
化させ、残留ＣＯ濃度を従来のものよりも大幅に低減さ
せることができ、小型の装置であっても高効率で水素を
精製することが可能となった。As a result, CO can be selectively oxidized without oxidizing hydrogen, and the residual CO concentration can be significantly reduced compared to conventional methods, making it possible to purify hydrogen with high efficiency even with a small device. It has become possible.
第１図は本発明を燃料電池による発電システムに応用し
た一実施例の概念図、第２図はその改質装置の部分の断
面図である。
又、図中の符号で１１は改質装置、１２は燃焼筒、ｌ３
はメタノール、１４は燃料電池本体、１５は燃焼室、１
６は燃焼触媒、１７は燃焼バーナ、２０は燃料供給管、
２１はメタノールタンク、２２は始動装置、２３はブロ
ワ、２４は燃焼用空気供給管、２５は蓄電池、２８は熱
交換筒、３１は水素原料予熱管、３２は水素原料供給管
、３３は水素原料加熱管、３６は水タンク、３７は水供
給管、３８は水、４１は改質用ヘッダ、４２は改質ガス
生成管、４６は改質用触媒、４７はＣＯ低減装置、４８
はＣＯシフト触媒、４９は水素極、５０は改質ガス供給
管、５３は発電機、５４は排気タービン、５５はＣＯ除
去装置、５６は燃焼用余剰ガス供給管、５７は酸素極、
５
９は反応用空気供給管である。FIG. 1 is a conceptual diagram of an embodiment in which the present invention is applied to a power generation system using a fuel cell, and FIG. 2 is a sectional view of a portion of the reformer. Also, in the figure, 11 is a reformer, 12 is a combustion tube, and l3
is methanol, 14 is the fuel cell body, 15 is the combustion chamber, 1
6 is a combustion catalyst, 17 is a combustion burner, 20 is a fuel supply pipe,
21 is a methanol tank, 22 is a starter, 23 is a blower, 24 is a combustion air supply pipe, 25 is a storage battery, 28 is a heat exchange cylinder, 31 is a hydrogen raw material preheating pipe, 32 is a hydrogen raw material supply pipe, 33 is a hydrogen raw material Heating pipe, 36 is a water tank, 37 is a water supply pipe, 38 is water, 41 is a reforming header, 42 is a reformed gas generation pipe, 46 is a reforming catalyst, 47 is a CO reduction device, 48
is a CO shift catalyst, 49 is a hydrogen electrode, 50 is a reformed gas supply pipe, 53 is a generator, 54 is an exhaust turbine, 55 is a CO removal device, 56 is a surplus gas supply pipe for combustion, 57 is an oxygen electrode, 5 9 is the reaction air supply pipe.
Claims (1)
水素原料から水素ガスを含む改質ガスを生成させる改質
装置と、この改質装置で生成した改質ガス中の一酸化炭
素を選択的に吸着除去するＣＯ低減装置と、このＣＯ低
減装置からの改質ガスに含まれる微量の一酸化炭素を更
に酸化除去するＣＯ除去装置とを具えた水素精製装置に
おいて、前記ＣＯ低減装置と前記ＣＯ除去装置との間の
改質ガス通路の途中にこれらＣＯ低減装置からＣＯ除去
装置へと流れる前記改質ガスにより回転する排気タービ
ンを有するエネルギ回収装置を設けたことを特徴とする
水素精製装置。Select a reformer that heats a hydrogen raw material and generates a reformed gas containing hydrogen gas from the hydrogen raw material through a reforming reaction accompanying this heating, and carbon monoxide in the reformed gas produced by this reformer. A hydrogen purification device comprising a CO reduction device that adsorbs and removes carbon dioxide, and a CO removal device that further oxidizes and removes trace amounts of carbon monoxide contained in the reformed gas from the CO reduction device. A hydrogen purification device characterized in that an energy recovery device having an exhaust turbine rotated by the reformed gas flowing from the CO reduction device to the CO removal device is provided in the middle of the reformed gas passage between the CO removal device and the CO removal device. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011828A JPH03218903A (en) | 1990-01-23 | 1990-01-23 | Hydrogen refiner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011828A JPH03218903A (en) | 1990-01-23 | 1990-01-23 | Hydrogen refiner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03218903A true JPH03218903A (en) | 1991-09-26 |
Family
ID=11788626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011828A Pending JPH03218903A (en) | 1990-01-23 | 1990-01-23 | Hydrogen refiner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03218903A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0652880A (en) * | 1992-07-28 | 1994-02-25 | Mitsubishi Electric Corp | Phosphoric acid type fuel cell power generating unit |
| EP0598530A1 (en) * | 1992-11-11 | 1994-05-25 | Vickers Shipbuilding & Engineering Limited | Processing of fuel gases, in particular for fuel cells and apparatus therefor |
| EP0671059A1 (en) * | 1993-08-20 | 1995-09-13 | Ballard Power Systems Inc. | Hydrocarbon fueled solid polymer fuel cell electric power generation system |
| JPH09147897A (en) * | 1995-11-17 | 1997-06-06 | Mitsubishi Heavy Ind Ltd | Solid high polymer fuel cell |
| JP2002154803A (en) * | 2000-11-15 | 2002-05-28 | Toyota Motor Corp | Gaseous hydrogen producing device |
-
1990
- 1990-01-23 JP JP2011828A patent/JPH03218903A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0652880A (en) * | 1992-07-28 | 1994-02-25 | Mitsubishi Electric Corp | Phosphoric acid type fuel cell power generating unit |
| EP0598530A1 (en) * | 1992-11-11 | 1994-05-25 | Vickers Shipbuilding & Engineering Limited | Processing of fuel gases, in particular for fuel cells and apparatus therefor |
| US5436086A (en) * | 1992-11-11 | 1995-07-25 | Vickers Shipbuilding & Engineering Limited | Processing of fuel gases, in particular for fuel cells and apparatus therefor |
| EP0671059A1 (en) * | 1993-08-20 | 1995-09-13 | Ballard Power Systems Inc. | Hydrocarbon fueled solid polymer fuel cell electric power generation system |
| EP0671059A4 (en) * | 1993-08-20 | 1999-05-26 | Ballard Power Systems | Hydrocarbon fueled solid polymer fuel cell electric power generation system. |
| JPH09147897A (en) * | 1995-11-17 | 1997-06-06 | Mitsubishi Heavy Ind Ltd | Solid high polymer fuel cell |
| JP2002154803A (en) * | 2000-11-15 | 2002-05-28 | Toyota Motor Corp | Gaseous hydrogen producing device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7399327B2 (en) | Direct water vaporization for fuel processor startup and transients | |
| JP3556638B2 (en) | Fuel cell device | |
| JP4979935B2 (en) | Fuel reformer | |
| JPH07315801A (en) | System for producing high-purity hydrogen, production of high-purity hydrogen and fuel cell system | |
| US20060143983A1 (en) | Apparatus for producing hydrogen gas and fuel cell system using the same | |
| CN106082127B (en) | Selective oxidation purifies the methanol steam reforming device of CO | |
| CN100542948C (en) | Hydrogen generator and working method thereof with double burner | |
| JP3530413B2 (en) | Fuel cell power generation system and operation method thereof | |
| JP2001223017A (en) | Fuel gas generating system for fuel cell | |
| JP4090234B2 (en) | Hydrogen-containing gas generator | |
| JPH03218903A (en) | Hydrogen refiner | |
| JP2670168B2 (en) | Hydrogen raw material reformer | |
| JP4008051B2 (en) | Power generation method | |
| JPH05129029A (en) | Power generation system formed by using fuel cell | |
| JP2003123815A (en) | Fuel cell system | |
| JP3697955B2 (en) | Catalytic combustor and method for raising temperature | |
| JPH03218902A (en) | Method for starting raw hydrogen material reformer | |
| JPS5826002A (en) | Steam reforming method and reaction tube for steam reforming | |
| JP2000327304A (en) | Hydrogen generation apparatus | |
| JP4128803B2 (en) | Fuel cell system | |
| JPH10338501A (en) | Power generating system of fuel cell | |
| JP2003317778A (en) | Exhaust gas combustor of fuel cell, and fuel cell power generation system | |
| JP2002326805A (en) | Reformer and fuel cell system which is equipped with this | |
| JP2000323163A (en) | Fuel reforming device | |
| JP2003303610A (en) | Fuel cell system and its operating method and auto- thermal reforming device |