A mixture of carbon monoxide and hydrogen gas obtained by reacting hot carbonaceous material with water vapor. When solid carbonaceous material is used as the raw material, the main reaction is: In the past, fuel gas was widely produced using coal and coke as raw materials, but since the second half of the 20th century, most production has shifted to using petroleum-based raw materials or reforming natural gas. The true water gasification reaction, which uses only steam as a gasification agent, is a large endothermic reaction, so as the reaction progresses, the temperature drops, the reaction rate slows, and the equilibrium shifts to the carbon dioxide production side (equation (2)). Therefore, various ideas have been devised to supply reaction heat. The supply of steam is stopped and switched to air, and some of the carbon is burned to raise the temperature. One example is the cyclic process, in which the supply of steam is switched back to steam when the temperature rises to obtain fuel gas. The gas obtained is mainly composed of 40% carbon monoxide and 50% hydrogen, and also contains carbon dioxide, methane, nitrogen, etc., with a calorific value of about 12 megajoules per cubic meter, which is too low for use as city gas. Such a cyclic process has many problems, such as poor operability, low carbon utilization rate, and cleanliness. Therefore, in modern coal gasification methods, in order to maintain the temperature inside the gasification furnace, a method is generally adopted in which not only steam but also oxygen is blown in at the same time to continuously gasify the gas. In the furnace, not only the water gasification reaction but also the combustion reaction, producer gas reaction, water gas shift reaction, etc. occur simultaneously. The composition of the generated gas varies depending on the reaction conditions. When water gas is used as a feedstock for chemical synthesis, the ratio of hydrogen to carbon monoxide is adjusted by the water-gas shift reaction: for example, to synthesize methanol, the hydrogen to carbon monoxide ratio is adjusted to 2:1, for methane it is adjusted to 3:1, and for ammonia it is converted entirely to hydrogen. [Akira Tomita] [References] | | | |Source: Shogakukan Encyclopedia Nipponica About Encyclopedia Nipponica Information | Legend |
高温の炭素質に水蒸気を作用させて得られる一酸化炭素と水素の混合ガス。固体の炭素質を原料とした場合の主反応は、 古くは、石炭、コークスを原料として盛んに燃料ガスを製造していたが、20世紀後半からはほとんどが石油系原料あるいは天然ガスの改質による方法に変わった。 ガス化剤として水蒸気だけを用いる真の意味の水性ガス化反応は大きな吸熱反応であるので、反応の進行とともに温度が低下し、反応速度が小さくなり、平衡が二酸化炭素生成側に傾く(式の(2))。そこで、反応熱を供給するための種々のくふうがなされてきた。水蒸気の供給を止めて空気に切り替え、一部の炭素分を燃焼させて温度を上昇させる。温度が上昇するとふたたび水蒸気に切り替えて燃料ガスを得るというサイクリックプロセスはその一例である。得られるガスは、一酸化炭素40%、水素50%が主成分で、ほかに二酸化炭素、メタン、窒素などが含まれる。発熱量は1立方メートル当り12メガジュール程度なので、都市ガスとして用いるには発熱量が低い。このようなサイクリックプロセスは、操作性の悪さ、炭素利用率の低さ、クリーンさなどの点で問題が多い。そこで近代的な石炭ガス化法では、ガス化炉内の温度を保つため、水蒸気だけでなく酸素も同時に吹き込んで、連続的にガス化する方法を一般には採用している。炉内では水性ガス化反応だけでなく、燃焼反応、発生炉ガス反応、水性ガスシフト反応などが併発することになる。生成ガス組成は反応条件によって異なる。 水性ガスを化学合成の原料として用いる場合には、水性ガスシフト反応によって水素と一酸化炭素の比を調整する。たとえば、メタノールを合成するには、水素と一酸化炭素比が2対1になるように、メタンの場合には3対1に、アンモニアの場合にはすべてを水素に変換する。 [富田 彰] [参照項目] | | | |出典 小学館 日本大百科全書(ニッポニカ)日本大百科全書(ニッポニカ)について 情報 | 凡例 |
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