Abstract：The preparation of hydrogen-rich reduction gas meeting the requirements of the direct reduction iron process is one of the key links to ensure the success of the direct reduction iron process, so it is important to solve the problem of the selection of the reduction gas preparation parameters. Based on the principle of material balance and chemical thermodynamic equilibrium, a "H-C-O system mass balance and chemical equilibrium diagram" (H-C-O balance diagram) was innovatively constructed and a graphical method to determine the process parameters of preparing hydrogen-rich reducing gas from the H-C-O balance diagram have been developed. The construction principle, including the design process of nH2O/nCH4 and nCO2/nCH4 scales, and how to use the graphical method of the H-C-O balance diagram are introduced. By using this graphical method, the position of any gas composition in the H-C-O balance diagram, the mol amount of H2O and CO2 that should be added to 1 mol CH4 gas when preparing the reduction gas with a given nH2/nCO composition, the source gas ratio for preparing any given gas composition, and the carbon deposition region for preparing hydrogen-rich reduction gas can be determined. In addition, an example for preparing hydrogen-rich reduction gas using the mixed gas(volume percent, for example 30%NG + 70%COG) of natural gas (NG) and coke oven gas (COG) as the gas source was taken in detail for determining the mol amount of the mixed gas of CO and CO2 to be added. Furthermore, a briefly introduction for the "critical carbon deposition curve" and "carbon deposition " region in the process of preparing hydrogen-rich reduction gas by reforming natural gas or coke oven gas is conducted and the influence of reforming temperature, total system pressure and nH2/nCO of the reduction gas on the critical carbon deposition curve and carbon deposition region are discussed. The abovementioned achievement provides a new theoretical and guiding basis for the selection of process parameters for the preparation of hydrogen-rich reduction gas from natural gas reforming or coke oven gas reforming.
沈峰满. H-C-O体系质量及化学平衡衡算图的开发[J]. 钢铁, 2023, 58(6): 12-17.
SHEN Fengman. Development of H-C-O system mass balance and chemical equilibrium diagram[J]. Iron and Steel, 2023, 58(6): 12-17.
[1] MOHSENZADEH F M, PAYAB H, ABEDI Z, et al. Reduction of CO2 emissions and energy consumption by improving equipment in direct reduction ironmaking plant[J]. Clean Technologies and Environmental Policy, 2019, 21(4): 847. [2] 沈峰满, 郑艾军, 郑海燕, 等.关于直接还原铁工艺及还原气制备的若干思考[J].钢铁,2022,57(3):10. (SHEN F M, ZHENG A J, ZHENG H Y, et al. Thoughts on preparation of hydrogen-based reduction gas and process of direct reduction iron[J]. Iron and Steel, 2022,57(3):10.) [3] 滕飞, 郭培民, 孔令兵, 等. 炼铁流程用氢减碳潜力分析[J].烧结球团,2022,47(1):18.(TENG F, GUO P M, KONG L B, et al. Potential analysis on carbon dioxide reduction with hydrogen in iron-making process[J]. Sintering and Pelletizing,2022,47(1):18.) [4] 苍大强. 钢铁工业“碳达峰”“碳中和”及低碳技术的误区及现实路径[J]. 中国冶金, 2021, 31(9): 3. (CANG D Q. Misunderstandings and realistic path of "carbon peak" "carbon neutrality" and low carbon technologies in iron and steel industry[J]. China Metallurgy, 2021, 31(9): 3.) [5] 张龙强, 陈剑. 钢铁工业实现“碳达峰”探讨及减碳建议[J]. 中国冶金, 2021, 31(9): 21. (ZHANG L Q, CHEN J. Discussion on achieving "carbon peak" and suggestions for reducing carbon in iron and steel industry[J]. China Metallurgy, 2021, 31(9): 21.) [6] 徐匡迪. 低碳经济与钢铁工业[J]. 钢铁, 2010, 45 (3): 1. (XU K D. Low carbon economy and iron and steel industry[J]. Iron and Steel, 2010, 45 (3): 1.) [7] 刘然, 张智峰, 刘小杰, 等. 低碳绿色炼铁技术发展动态及展望[J]. 钢铁, 2022, 57(5): 1. (LIU R, ZHANG Z F, LIU X J, et al. Development trend and prospect of low-carbon green ironmaking technology[J]. Iron and Steel, 2022, 57(5): 1.) [8] 王新东,郝良元. 现代炼铁工艺及低碳发展方向分析[J]. 中国冶金,2021,31(5):1.(WANG X D, HAO L Y. Analysis of modern ironmaking process and low-carbon development direction[J]. China Metallurgy, 2021,31(5):1.) [9] KOPFLE J, HUNTER R. Direct reduction′s role in the world steel industry[J]. Ironmaking and Steelmaking, 2008, 35(4): 254. [10] 周渝生, 钱晖, 齐渊洪, 等. 煤制气生产直接还原铁的联合工艺方案[J].钢铁,2012,47(11):27.(ZHOU Y S, QIAN H, QI Y H, et al. Scheme of direct reduction iron production combined with coal gasification[J].Iron and Steel, 2012, 47(11):27.) [11] ZHU D Q, QIU G Z, JIANG T, et al. An innovative process for direct reduction of cold-bound pellets from iron concentrate with a coal-based rotary kiln[J]. Journal of Central South University of Technology, 2000, 7(2): 68. [12] BAIKADI A, RUNKANA V, SUBRAMANIAN S. Operability analysis of direct reduction of iron ore by coal in an industrial rotary kiln[J]. IFAC-Papers on Line, 2016, 49(1): 468. [13] INADA Y. Improvements in the MIDREX direct reduction process[J]. Research and Development Kobe Steel Engineering Reports, 2000, 50(3): 86. [14] CHEELEY R, LEU M. Coal gasification for DRI production-An Indian solution[J]. Steel Times International, 2010, (4):1. [15] 董跃, 乔星星, 刘改换, 等. 气基直接还原铁工艺还原气研究现状[J]. 能源与节能, 2016(3): 2.(DONG Y, QIAO X X, LIU G H, et al. Research situation of reduction gas used in gas-based direct reduction iron technology[J]. Energy and Energy Conservation, 2016(3): 2.) [16] 张福明, 曹朝真, 徐辉. 气基竖炉直接还原技术的发展现状与展望[J]. 钢铁, 2014, 49(3): 1.(ZHANG F M, CAO C Z, XU H. Current status and prospects of gas-based shaft furnace direct reduction technology[J]. Iron and Steel, 2014,49(3):1.) [17] 于恒, 周继程, 郦秀萍, 等. 气基竖炉直接还原炼铁流程重构优化[J]. 中国冶金, 2021, 31(1):31.(YU H, ZHOU J C, LI X P, et al. Reconstruction optimization of gas-based shaft furnace direct reduction ironmaking process[J]. China Metallurgy, 2021, 31(1):31.) [18] 车彦民,曹莉霞,刘金哲. 氢的大规模制备及在钢铁行业的应用和展望[J]. 中国冶金, 2022, 32(9): 1(CHE Y M,CAO L X, LIU J Z. Large scale hydrogen production and its application and prospect in iron and steel industry[J]. China Metallurgy,2022, 32(9): 1.) [19] 郑少波. 氢冶金基础研究及新工艺探索[J]. 中国冶金, 2012, 22(7): 1(ZHENG S B. Basic research on hydrogen metallurgy and new ironmaking idea-process[J]. China Metallurgy,2012, 22(7): 1.) [20] 陈健,苏敏,张新波,等. 氢冶金还原性气体的制备研究进展[J]. 中国冶金,2023,33(1):24.(CHEN J, SU M, ZHANG X B, et al. Research progress in preparation of reducing gases for hydrogen metallurgy[J]. China Metallurgy, 2023, 33(1):24.) [21] 张福明, 银光宇, 李欣. 现代高炉高风温关键技术问题的认识与研究[J]. 中国冶金, 2020, 30(12): 1. (ZHANG F M, YIN G Y, LI X. Research and cognition on key technical problems of high blast temperature for modern blast furnace[J]. China Metallurgy, 2020, 30(12): 1.) [22] 金永龙, 何志军, 王川. 不同炉料结构高炉实现低碳排放的解析[J]. 钢铁, 2019, 54(7): 8. (JIN Y L,HE Z J,WANG C. Analysis on low carbon emission of blast furnace with different raw materials structure[J]. Iron and Steel, 2019, 54(7): 8.) [23] 王新东, 金永龙. 高炉使用高比例球团的战略思考与球团生产的试验研究[J]. 钢铁, 2021, 56(5): 7. (WANG X D, JIN Y L. Strategy analysis and testing study of high ratio of pellet utilized in blast furnace[J]. Iron and Steel, 2021, 56(5): 7.) [24] 张福明, 颉建新. 冶金流程工程学的典型应用[J]. 钢铁, 2021, 56(8): 10. (ZHANG F M, XIE J X. Typical application of metallurgical process engineering[J]. Iron and Steel, 2021, 56(8): 10.) [25] SUN G Y, YANG W S, GUO J, et al. Analysis of energy consumption of the reduction of Fe2O3 by hydrogen and carbon monoxide mixtures[J].Energies, 2020, 13(8): 1986. [26] SHIGEYUKI U, NOBORU S, HIROSHI A, et al. Steam reforming of methane in a hydrogen-permeable membrane reactor[J]. Applied Catalysis, 1991, 67(1): 223. [27] ÖZTÜRK M, ÖZEK N, YÜKSEL Y E. Hydrogen production from natural gas and captures of carbon dioxide emissions[J]. SDU International Journal of Technologic Sciences, 2010, 2(2): 1. [28] 梁之凯,黄柱成,易凌云.焦炉煤气竖炉法生产DRI的煤气用量及利用率[J].中国冶金,2017,27(11):18.(LIANG Z K, HUANG Z C, YI L Y. Coke oven gas consumption and its utilization ratio for DRI production in shaft furnace[J]. China Metallurgy,2017,27(11):18. [29] 沈峰满. 一种用于制备氢基还原气的工艺参数确定方法:中国, ZL202110727435.6[P]. 2021-06-29.(SHEN F M. A Method for Determining Process Parameters for Preparing Hydrogen-Based Reducing Gas: China, ZL202110727435.6[P]. 2021-06-29.) [30] 沈峰满, 章苇玲, 郑艾军, 等.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法的应用例[J/OL].钢铁:1[2023-04-04]. https://doi.org/10.13228/j.boyuan.issn0449-749x.20220750. (SHEN F M, ZHANG W L, ZHENG A J, et al. Regulation of carbon deposition during the 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:1[2023-04-04]. https://doi.org/10.13228/j.boyuan.issn0449-749x.20220750.)
2023, Vol. 58 
