关于天然气重整制备富氢还原气体过程中析碳问题的调控——H-C-O体系质量及化学平衡衡算图的应用例

doi:10.13228/j.boyuan.issn0449-749x.20220750

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摘要采用天然气重整或焦炉煤气重整工艺制备富氢还原气体时,若操作参数控制不当将会出现碳的析出问题,影响制备富氢气体工序的稳定顺行,因此研究控制制备富氢还原气体过程中的析碳非常必要。应用“H-C-O体系质量及化学平衡衡算图”和化学平衡原理,探讨了天然气重整或焦炉煤气重整工艺制备富氢还原气体过程中的“析碳”问题。在假设天然气重整或焦炉煤气重整体系处于临界析碳状态的前提下,确定了析碳曲线与还原气体n_H₂/n_CO、重整温度和体系总压等因素的对应关系,从热力学角度给出了天然气重整或焦炉煤气重整制备富氢还原气体工艺中的临界析碳曲线、“析碳区”与“非析碳区”以及控制析碳且能满足直接还原铁要求的给定n_H₂/n_CO值富氢还原气体制备时的重整温度与体系总压等工艺参数。结果表明,为了确保n_H₂/n_CO和有效成分φ(H₂)+φ(CO)合量同时满足直接还原气体组成要求,在体系总压P_tot=0.1 MPa条件下重整温度须高于800 ℃;随着体系总压的升高,CH₄的转化率呈下降趋势;对于低n_H₂/n_CO(=2),随着体系总压的升高析碳区域将增大;但对于n_H₂/n_CO(=5),随着体系总压的升高析碳区域反而变小,这是因为当n_H₂/n_CO较低时,碳的气化反应为主流反应,提高压力将增强析碳,而当n_H₂/n_CO较高时,甲烷分解反应为主流反应,压力升高将妨碍甲烷分解,抑制了析碳的缘故;另外,体系总压过高将无法获得有效成分φ(H₂)+φ(CO)合量满足直接还原铁工艺要求的还原气体。

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	沈峰满
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关键词 ：富氢直接还原铁, 富氢还原气体, 天然气重整或焦炉煤气重整, H-C-O体系质量及化学平衡衡算图, 析碳控制, 热力学分析

Abstract：If the operating parameters in the process of preparing hydrogen-rich reducing gas are not properly controlled, the problem of carbon deposition will occur, which will affect the stability of the process of preparing hydrogen-rich reducing gas by using natural gas or coke oven gas as the gas source. Therefore, it is necessary to investigate and control the problem of carbon deposition in the process of preparing hydrogen-rich reducing gas that meets the requirements of the direct reduction iron process. The problem of "carbon deposition" in the process of preparing hydrogen-rich reducing gas from natural gas reforming or coke oven gas reforming process was discussed by using the "H-C-O system mass and chemical balance diagram" and the principle of chemical equilibrium. Assuming that the natural gas reforming or coke oven gas reforming system is at the critical state of carbon deposition, the relationships between the carbon deposition curve and the factors of n_H₂/n_CO of the reduction gas, reforming temperature, and total system pressure were determined, the critical carbon deposition curve in the process of reforming natural gas or coke oven gas to hydrogen-rich reducing gas was given from the perspective of thermodynamics, the "carbon deposition region" and "non-carbon deposition region" were obtained, and the process parameters, such as the reforming temperature of hydrogen-rich reducing gas and the total system pressure, which can inhibit the carbon deposition and meet the required n_H₂/n_CO of direct reduction iron, were given. The results show that in order to ensure n_H₂/n_CO and the total amount of the effective composition of φ(H₂)+φ(CO)simultaneously meet the requirements for the composition of the direct reduction gas, the reforming temperature must be higher than 800 ℃ under P_tot=0.1 MPa; The conversion of CH₄ decreased with the increase of total system pressure; For low n_H₂/n_CO (=2), the carbon deposition region will increase with the increase of the total system pressure and for n_H₂/n_CO (=5), with the increase of the total pressure of the system, the carbon deposition region becomes smaller, which is because the gasification reaction of carbon is the mainstream reaction when n_H₂/n_CO is low and increasing the total system pressure will enhance the carbon deposition; However, when n_H₂/n_CO is high, the methane decomposition reaction is the mainstream reaction, and increasing pressure rise will hinder the methane decomposition and inhibit the carbon deposition. In addition, if the total system pressure is too high, it will not be able to obtain the reducing gas with the effective composition of φ(H₂)+φ(CO) to meet the requirements of the direct reduction iron process.

Key words： hydrogen-rich direct reduction iron hydrogen-rich reducing gas natural gas reforming or coke oven gas reforming H-C-O system mass balance and chemical equilibrium diagram control of carbon deposition thermodynamic analysis

收稿日期: 2022-12-06

引用本文:

沈峰满, 章苇玲, 郑艾军, 郑海燕, 丁智敏, 李季. 关于天然气重整制备富氢还原气体过程中析碳问题的调控——H-C-O体系质量及化学平衡衡算图的应用例[J]. 钢铁, 2023, 58(7): 9-16. SHEN Fengman, ZHANG Weiling, ZHENG Aijun, ZHENG Haiyan, DING Zhimin, LI Ji. Regulation of carbon deposition during preparation process of hydrogen-rich reducing gas by natural gas reforming ——An application example of H-C-O system mass balance and chemical equilibrium diagram[J]. Iron and Steel, 2023, 58(7): 9-16.

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