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

doi:10.3969/j.issn.0438-1157.2014.06.003

Abstract

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

CLC Number:

TQ116.2

WU Rong, WU Sufang. Thermodynamic calculations for reactive sorption enhanced reforming of C2/C3 light hydrocarbons[J]. CIESC Journal, 2014, 65(6): 1961-1970.

吴嵘, 吴素芳. 反应吸附强化C2/C3烃水蒸气重整制氢反应热力学计算[J]. 化工学报, 2014, 65(6): 1961-1970.

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