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The water-gas shift reaction (WGSR) describes the reaction of carbon monoxide and water vapor to form carbon dioxide and hydrogen (the mixture of carbon monoxide and hydrogen is known as water gas): : CO + H2O CO2 + H2 The water gas shift reaction was discovered by Italian physicist Felice Fontana in 1780. It was not until much later that the industrial value of this reaction was realized. Before the early 20th century, hydrogen was obtained by reacting steam under high pressure with iron to produce iron, iron oxide and hydrogen. With the development of industrial processes that required hydrogen, such as the Haber–Bosch ammonia synthesis, the demand for a less expensive and more efficient method of hydrogen production was needed.〔 As a resolution to this problem, the WGSR was combined with the gasification of coal to produce a pure hydrogen product. As the ideal of hydrogen economy gains popularity, the focus on hydrogen as a replacement fuel source for hydrocarbons is increasing. ==Applications== The WGSR is an important industrial reaction that is used in the manufacture of ammonia, hydrocarbons, methanol, and hydrogen. It is also often used in conjunction with steam reforming of methane and other hydrocarbons. In the Fischer–Tropsch process, the WGSR is one of the most important reactions used to balance the H2/CO ratio. It provides a source of hydrogen at the expense of carbon monoxide, which is important for the production of high purity hydrogen for use in ammonia synthesis. The water-gas shift reaction may be an undesired side reaction in processes involving water and carbon monoxide, e.g. the rhodium-based Monsanto process. The iridium-based Cativa process uses less water, which suppresses this reaction. The equilibrium of this reaction shows a significant temperature dependence and the equilibrium constant decreases with an increase in temperature, that is, higher carbon monoxide conversion is observed at lower temperatures. In order to take advantage of both the thermodynamics and kinetics of the reaction, the industrial scale water gas shift reaction is conducted in multiple adiabatic stages consisting of a high temperature shift (HTS) followed by a low temperature shift (LTS) with intersystem cooling.〔 The initial HTS takes advantage of the high reaction rates, but is thermodynamically limited, which results in incomplete conversion of carbon monoxide and a 2-4% carbon monoxide exit composition. To shift the equilibrium toward hydrogen production, a subsequent low temperature shift reactor is employed to produce a carbon monoxide exit composition of less than 1%. The transition from the HTS to the LTS reactors necessitates intersystem cooling. Due to the different reaction conditions, different catalysts must be employed at each stage to ensure optimal activity. The commercial HTS catalyst is the iron oxide–chromium oxide catalyst and the LTS catalyst is a copper-based catalyst. The order proceeds from high to low temperature due to the susceptibility of the copper catalyst to poisoning by sulfur that may remain after the steam reformation process.〔 This necessitates the removal of the sulfur compounds prior to the LTS reactor by a guard bed in order to protect the copper catalyst. Conversely, the iron used in the HTS reaction is generally more robust and resistant toward poisoning by sulfur compounds. While both the HTS and LTS catalysts are commercially available, their specific composition varies based on vendor. An important limitation for the HTS is the H2O/CO ratio where low ratios may lead to side reactions such as the formation of metallic iron, methanation, carbon deposition, and Fischer–Tropsch reaction. 抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)』 ■ウィキペディアで「Water-gas shift reaction」の詳細全文を読む スポンサード リンク
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