CIESC Journal ›› 2014, Vol. 65 ›› Issue (6): 1961-1970.DOI: 10.3969/j.issn.0438-1157.2014.06.003

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Thermodynamic calculations for reactive sorption enhanced reforming of C2/C3 light hydrocarbons

WU Rong1, WU Sufang1,2   

  1. 1. Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China;
    2. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2013-09-06 Revised:2013-12-13 Online:2014-06-05 Published:2014-06-05

反应吸附强化C2/C3烃水蒸气重整制氢反应热力学计算

吴嵘1, 吴素芳1,2   

  1. 1. 浙江大学化学工程与生物工程学系, 浙江 杭州 310027;
    2. 浙江大学生物质化工教育部重点实验室, 浙江 杭州 310027
  • 通讯作者: 吴素芳
  • 作者简介:吴嵘(1981- ),男,博士研究生。

Abstract: In order to extend the use of raw materials of reactive sorption enhanced reforming process (ReSER) for hydrogen production, a thermodynamic analysis on cock oven gas (COG) containing C2/C3 light hydrocarbons, such as C2H4, C2H6, C3H6, and C3H8, were carried out for the feasibility and optimization operation conditions by using simulation software Aspen Plus. The calculations are based on the system pressure of 0.1-5 MPa, reaction temperature of 200-800℃, steam to carbon molar ratio (S/C) of 1-8, and calcium oxide to carbon molar ratio (Ca/C) of 0-5. The calculation results show that the products with over 95% H2 can be obtained by ReSER process using COG as raw materials under the optimized reaction conditions of S/C of 4, Ca/C of 2.5, reaction temperature between 200℃ and 650℃, and system pressure between 0.1 and 1.8 MPa. The H2 content in products increases with the increase of S/C or Ca/C. For selected CO2 removal ratio over 0.9, the H2 molar fraction is over 95% when the reaction temperature of C2H4, C2H6, C3H6 and C3H8 is over 250℃, 400℃, 250℃ and 350℃ respectively, at S/C of 4 and Ca/C of 2.5. For CO2 removal ratio lower than 0.9, the reaction temperature of C2H4, C2H6, C3H6 and C3H8 should be 50℃ higher for H2 molar fraction more than 95%. Among hydrocarbons with the same C number, it is easier for alkenes to present ReSER process than alkanes. The raw material with more C number is more easily to have ReSER process.

Key words: hydrogen production, hydrocarbons, enhanced reactive sorption, steam reforming, thermodynamics

摘要: 为拓宽反应吸附强化水蒸气重整制氢(ReSER)原料的应用范围,采用化工流程模拟软件Aspen Plus,针对包括C2H4、C2H6、C3H6、C3H8 的C2/C3轻烃 ReSER制氢反应可行性和优化条件进行热力学分析计算。在选择的反应压力0.1~5 MPa,温度200~800℃,水碳摩尔比(S/C)1~8和吸附剂中氧化钙和原料碳摩尔比(Ca/C)0~5条件下进行热力学分析计算。计算结果表明:在优选的水碳比(S/C)4,钙碳比(Ca/C)2.5,温度200~650℃,压力0.1~1.8 MPa的条件下, C2H4、C2H6、C3H6、C3H8均可分别通过ReSER反应获得H2含量在95%以上的产物,产物中H2浓度均随着水碳比和钙碳比的增大而提高。在假设的水碳比4,钙碳比2.5条件下,当CO2脱除率达到0.9以上,C2H4、C2H6、C3H6、C3H8的反应温度分别高于250、400、250、350℃时,产物中H2摩尔分数均可达到95%以上,产物中的H2浓度随着反应温度的升高和CO2脱除率的增加而提高。当CO2脱除率低于0.9,产物H2摩尔分数要达到95%时,C2H4、C2H6、C3H6、C3H8的反应温度均需升高50℃。在相同长度C链的烃类中,烯烃比烷烃更容易发生ReSER反应。而原料的碳链越长,则越容易发生ReSER制氢反应。

关键词: 制氢, 碳氢化合物, 反应吸附强化, 水蒸气重整, 热力学

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