JP4666127B2 - Methanol reforming reactor - Google Patents
Methanol reforming reactor Download PDFInfo
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- JP4666127B2 JP4666127B2 JP2001105531A JP2001105531A JP4666127B2 JP 4666127 B2 JP4666127 B2 JP 4666127B2 JP 2001105531 A JP2001105531 A JP 2001105531A JP 2001105531 A JP2001105531 A JP 2001105531A JP 4666127 B2 JP4666127 B2 JP 4666127B2
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Description
【0001】
【発明の属する技術分野】
本発明は、メタノールと水を小型装置で効率良く反応させて水素ガスを製造するメタノール改質反応器に関する。
【0002】
【従来の技術】
水素ガスは、石油精製工業での改質、脱硫用、化学工業での各種合成、水添用等、多くの産業分野で使用されており、最近では電子産業、食品工業、燃料電池用等の新規分野での利用が加わり、その使用分野が増大している。
メタノールを原料とする水素ガスの製造は、原料のメタノールの輸送および貯蔵が容易であること、比較的低い温度で反応が容易に行われること等から、最近では水素を消費する装置に隣接してメタノール改質装置を設置し、無人化運転を行うことが検討されている。
このメタノール改質用反応器には通常、多管式熱交換器が用いられ、反応管の内部に触媒を充填して外部より燃焼ガス、熱媒油および水蒸気などで加熱する方式が採られているが、できるだけ小型の装置で効率良く反応を行うために、例えば特開昭61-286204号公報、特開昭62-160134号公報、特開昭63-166701号公報等にはプレート型熱交換器を用いることが記載されており、特開昭63-25201号公報にはスパイラル型熱交換器を用いることが記載されている。また、特開平3-60401号公報には複数個のU字型反応管を設置し、胴側に熱媒油を供給して加熱する装置が記載されている。
【0003】
【発明が解決しようとする課題】
前述の熱交換器で加熱する方法では、一般には熱媒油が用いられている。この方法では、多量の熱媒油を必要とするので、起動時に時間を要し、また、発生水素量が多い場合には装置が大型化し、現実的ではない。
本発明の目的は、小型であり、かつ高発生水素量のメタノール改質用反応器を提供することである。
【0004】
【課題を解決するための手段】
発明者等は上記の如き課題を有するメタノール改質反応器について鋭意検討した結果、熱媒油の蒸発潜熱を利用して原料を加熱することにより、従来の顕熱のみを利用した場合に比べ熱媒油の使用量が少なく、小型で高発生水素量のメタノール改質反応器が得られることを見出し、本発明に到達した。
即ち本発明は、メタノールと水の混合蒸気を触媒の存在下に反応させるメタノール改質用反応器において、メタノールと水を加熱する際に、熱源として熱媒油の蒸気を使用することを特徴とするメタノール改質用反応器に関するものである。
【0005】
【発明の実施の形態】
メタノール改質装置では、原料であるメタノールおよび水を加熱、蒸発させ、触媒と接触させ、次式に示されるメタノール改質反応を進行させ、水素を発生させる。この反応が吸熱反応であるため、加熱して反応を促進させることで効率的な反応を行うことができる。また、反応生成物は未反応メタノール等を回収後、水素精製設備に送られ、高純度水素と排ガスとに分離される。
CH3OH + H2O = CO2+ 2H2 (1)
CO2 + H2 = CO + H2O (2)
【0006】
本発明では、メタノールと水を加熱するための熱源として、熱媒油の蒸気を用いる。即ち、熱媒油を蒸発させ、その蒸気と反応系との熱交換を行う。ここでは熱媒油の蒸発潜熱を利用するため、顕熱のみ利用する場合に比べ、単位熱媒油量当りの熱交換量が大きいので、熱媒油の使用量が少なくて済む。従って、装置も小型化することができる。
また、潜熱と顕熱を同時利用することもできる。
【0007】
本発明で使用する熱媒油は、使用温度での変性が少なく、メタノール改質反応温度以下で蒸気を発生するものであれば特に制限されないが、サームS(商品名、新日鐡化学(株)製)等が好適である。
熱媒油の加熱方法は特に制限されないが、電気ヒーターを用いると温度制御が容易であり好適に実施できる。また、前述の水素精製設備で発生する排ガスを燃焼させ、その燃焼熱を利用することもできる。
【0008】
メタノールおよび水を加熱、蒸発させる方法は特に制限されないが、熱媒油やその蒸気を用いると好適である。
また、熱媒油や、改質反応で生成した分解ガスにより、反応器に供給するメタノールおよび水を予熱することもできる。
【0009】
本発明のメタノール改質反応は、230〜300℃の温度で実施される。
供給するメタノールと水のモル比は、1:1〜1:10の範囲である。
触媒としては種々のメタノール改質用触媒を使用できる。
反応器の形式は、熱媒油蒸気との熱交換が可能な構造であれば特に制限されない。例えば、U字型反応管や直管式反応器を用いることができる。
【0010】
次に図を用いて本発明を説明する。
図1は本発明のメタノール改質用反応器の一例である。
図1において、メタノールと水の混合物は反応器内に設置された原料過熱器を経由し反応器に供給される。その際、該混合物はスーパーヒート状態となり、触媒を充填したU字型反応管に導入され、改質反応が行われる。
一方、熱媒油槽の熱媒油は電気ヒーターにより加熱され、蒸発した熱媒油は前述の混合物と熱交換され、凝縮した熱媒油は熱媒油槽に戻る。熱媒油の加熱に、水素精製設備で発生した排ガスの燃焼ガスを利用することでエネルギーの有効利用ができる。
【0011】
【実施例】
次に実施例により本発明を更に具体的に説明する。但し本発明はこの実施例により制限されるものではない。
【0012】
実施例1
図1に示される改質用反応器の熱交換部に銅系触媒を充填し、熱媒油(サームS)300リットルを熱媒油槽に仕込んだ。
メタノールと水の混合蒸気(モル比1:2)を、圧力0.8MPa、温度260℃、流量25Nm3/Hで供給した。一方、熱媒油を電気ヒーターで260℃に加熱、蒸発させ、熱媒油蒸気と前述のメタノールと水の混合蒸気とで熱交換を行いながら連続的に水素を製造した。メタノールの分解率は100%であり、分解ガス中のCO濃度は0.8%以下であった。
【0013】
特開平3-60401号公報に記載された、熱媒油の顕熱のみを利用する装置では、実施例1と同じ処理量を得るためには、熱媒油を約3000リットル要する。
本発明では約1/10の熱媒油量で処理することができる。
【0014】
【発明の効果】
本発明により、熱媒油の蒸発潜熱を利用して、メタノール改質反応を行うと、熱媒油の使用量が少なく、装置も小型化できる。
従って本発明のメタノール改質用反応器は工業的に極めて有利な装置である。
【図面の簡単な説明】
【図1】図1は本発明のメタノール改質用反応器の一例である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a methanol reforming reactor for producing hydrogen gas by efficiently reacting methanol and water with a small apparatus.
[0002]
[Prior art]
Hydrogen gas is used in many industrial fields such as reforming in the oil refining industry, desulfurization, various synthesis in the chemical industry, hydrogenation, etc. Recently, it is used in the electronics industry, food industry, fuel cell, etc. The use in new fields is added, and the fields of use are increasing.
The production of hydrogen gas using methanol as a raw material has recently been adjacent to an apparatus that consumes hydrogen because of the ease of transport and storage of the raw material methanol and the ease of reaction at relatively low temperatures. Installation of a methanol reformer to conduct unmanned operation is being studied.
A multi-tubular heat exchanger is usually used for the methanol reforming reactor, and a system in which a catalyst is filled in the reaction tube and heated with combustion gas, heat transfer oil, steam, etc. from outside is adopted. However, in order to perform the reaction efficiently with a device as small as possible, for example, JP-A-61-286204, JP-A-62-160134, JP-A-63-166701, etc. The use of a heat exchanger is described, and JP-A 63-25201 describes the use of a spiral heat exchanger. Japanese Patent Application Laid-Open No. 3-60401 describes an apparatus in which a plurality of U-shaped reaction tubes are installed, and heat medium oil is supplied to the barrel side to heat.
[0003]
[Problems to be solved by the invention]
In the method of heating with the heat exchanger described above, a heat transfer oil is generally used. Since this method requires a large amount of heat transfer oil, it takes time at startup, and when the amount of generated hydrogen is large, the apparatus becomes large, which is not practical.
An object of the present invention is to provide a methanol reforming reactor that is small in size and has a high hydrogen generation amount.
[0004]
[Means for Solving the Problems]
As a result of intensive studies on the methanol reforming reactor having the above-mentioned problems, the inventors have heated the raw material using the latent heat of vaporization of the heat transfer oil, so that the heat is higher than when only sensible heat is used. The present inventors have found that a methanol reforming reactor with a small amount of a medium oil used and a small amount of hydrogen generated can be obtained.
That is, the present invention is characterized in that in a methanol reforming reactor in which a mixed steam of methanol and water is reacted in the presence of a catalyst, the steam of heat transfer oil is used as a heat source when the methanol and water are heated. The present invention relates to a methanol reforming reactor.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the methanol reformer, methanol and water as raw materials are heated and evaporated, brought into contact with a catalyst, and a methanol reforming reaction represented by the following formula proceeds to generate hydrogen. Since this reaction is an endothermic reaction, an efficient reaction can be performed by heating to promote the reaction. Further, the reaction product collects unreacted methanol and the like, and is then sent to a hydrogen purification facility where it is separated into high-purity hydrogen and exhaust gas.
CH 3 OH + H 2 O = CO 2 + 2H 2 (1)
CO 2 + H 2 = CO + H 2 O (2)
[0006]
In the present invention, steam of heat transfer oil is used as a heat source for heating methanol and water. That is, the heat transfer oil is evaporated and heat exchange between the steam and the reaction system is performed. Since the latent heat of vaporization of the heat transfer oil is used here, the amount of heat transfer oil used per unit heat transfer oil is larger than when only sensible heat is used. Therefore, the apparatus can also be reduced in size.
Also, latent heat and sensible heat can be used simultaneously.
[0007]
The heat transfer oil used in the present invention is not particularly limited as long as it is less denatured at the use temperature and generates steam at or below the methanol reforming reaction temperature, but therm S (trade name, Nippon Steel Chemical Co., Ltd.) Etc.) are suitable.
The heating method of the heat transfer oil is not particularly limited, but when an electric heater is used, temperature control is easy and can be suitably performed. It is also possible to burn the exhaust gas generated in the above-described hydrogen purification equipment and use the combustion heat.
[0008]
The method for heating and evaporating methanol and water is not particularly limited, but it is preferable to use heat transfer oil or its vapor.
In addition, methanol and water supplied to the reactor can be preheated by heat medium oil or cracked gas generated by the reforming reaction.
[0009]
The methanol reforming reaction of the present invention is carried out at a temperature of 230 to 300 ° C.
The molar ratio of methanol to water supplied is in the range of 1: 1 to 1:10.
As the catalyst, various methanol reforming catalysts can be used.
The type of the reactor is not particularly limited as long as it has a structure capable of heat exchange with the heat transfer oil vapor. For example, a U-shaped reaction tube or a straight tube reactor can be used.
[0010]
Next, the present invention will be described with reference to the drawings.
FIG. 1 is an example of a methanol reforming reactor of the present invention.
In FIG. 1, a mixture of methanol and water is supplied to the reactor via a raw material superheater installed in the reactor. At that time, the mixture is in a superheated state, introduced into a U-shaped reaction tube filled with a catalyst, and a reforming reaction is performed.
On the other hand, the heat medium oil in the heat medium oil tank is heated by an electric heater, the evaporated heat medium oil is heat-exchanged with the aforementioned mixture, and the condensed heat medium oil returns to the heat medium oil tank. By using the combustion gas of the exhaust gas generated in the hydrogen refining equipment for heating the heat transfer oil, energy can be effectively used.
[0011]
【Example】
Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by this embodiment.
[0012]
Example 1
The heat exchange part of the reforming reactor shown in FIG. 1 was filled with a copper-based catalyst, and 300 liters of heat transfer oil (Therm S) was charged into the heat transfer oil tank.
A mixed vapor of methanol and water (molar ratio 1: 2) was supplied at a pressure of 0.8 MPa, a temperature of 260 ° C., and a flow rate of 25 Nm 3 / H. On the other hand, heat medium oil was heated to 260 ° C. with an electric heater and evaporated, and hydrogen was continuously produced while heat exchange was performed between the heat medium oil vapor and the above-described mixed vapor of methanol and water. The decomposition rate of methanol was 100%, and the CO concentration in the cracked gas was 0.8% or less.
[0013]
In the apparatus described in Japanese Patent Laid-Open No. 3-60401 that uses only the sensible heat of the heat transfer oil, about 3000 liters of the heat transfer oil is required to obtain the same processing amount as in the first embodiment.
In the present invention, it can be processed with a heat medium oil amount of about 1/10.
[0014]
【The invention's effect】
According to the present invention, when the methanol reforming reaction is performed using the latent heat of vaporization of the heat transfer oil, the amount of heat transfer oil used is small and the apparatus can be downsized.
Therefore, the methanol reforming reactor of the present invention is an industrially extremely advantageous apparatus.
[Brief description of the drawings]
FIG. 1 is an example of a methanol reforming reactor according to the present invention.
Claims (6)
Priority Applications (1)
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JP2001105531A JP4666127B2 (en) | 2001-04-04 | 2001-04-04 | Methanol reforming reactor |
Applications Claiming Priority (1)
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JP2001105531A JP4666127B2 (en) | 2001-04-04 | 2001-04-04 | Methanol reforming reactor |
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JP2002293507A JP2002293507A (en) | 2002-10-09 |
JP4666127B2 true JP4666127B2 (en) | 2011-04-06 |
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JP2001105531A Expired - Fee Related JP4666127B2 (en) | 2001-04-04 | 2001-04-04 | Methanol reforming reactor |
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JP2011102658A (en) * | 2009-11-10 | 2011-05-26 | Jfe Steel Corp | Method of recovering sensible heat from exhaust gas generated from metallurgical furnace and method of cooling exhaust gas generated from metallurgical furnace |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54100549A (en) * | 1978-01-23 | 1979-08-08 | Sharp Corp | Storage type electric water boiler |
JPH0360401A (en) * | 1989-07-27 | 1991-03-15 | Mitsubishi Gas Chem Co Inc | Methanol reforming reactor |
JPH06287001A (en) * | 1993-03-31 | 1994-10-11 | Nippon Sanso Kk | Production of hydrogen and carbon dioxide |
JPH0881202A (en) * | 1994-09-13 | 1996-03-26 | Toyota Motor Corp | Methanol reformer for fuel cell |
-
2001
- 2001-04-04 JP JP2001105531A patent/JP4666127B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54100549A (en) * | 1978-01-23 | 1979-08-08 | Sharp Corp | Storage type electric water boiler |
JPH0360401A (en) * | 1989-07-27 | 1991-03-15 | Mitsubishi Gas Chem Co Inc | Methanol reforming reactor |
JPH06287001A (en) * | 1993-03-31 | 1994-10-11 | Nippon Sanso Kk | Production of hydrogen and carbon dioxide |
JPH0881202A (en) * | 1994-09-13 | 1996-03-26 | Toyota Motor Corp | Methanol reformer for fuel cell |
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