太阳能甲烷干重整复杂反应体系的热化学储能特性

doi:10.16085/j.issn.1000-6613.2019-0375

摘要/Abstract

摘要：

基于热力学第一和第二定律对太阳能甲烷干重整复杂反应体系的热力学特性进行建模分析，研究该体系在不同太阳光照强度时的反应器温度响应及热化学储能特性，以及副反应和各部分能量损失对整个体系能量效率的影响规律。通过平衡常数法计算反应器平衡状态时的物质组成，并进而利用热力学模型计算不同条件下入口气转化率、选择性、功效率和能量转换效率的变化规律。结果表明：进料比n(CO₂)/n(CH₄)的升高有助于提高甲烷转化率、选择性、功效率和能量转换效率；反应器温度的变化对系统热化学储能特性的影响显著，在较低温区（923～1123K），副反应较多，且随着温度的升高副反应逐渐受到抑制，积炭减少，功效率和能量转换效率逐渐升高，并在1123K时达到峰值；温度继续升高（>1123K），反应器辐射损失显著增加，导致功效率和能量转换效率随温度升高而降低；高温区（>1200K），副反应受到抑制，复杂反应体系的系统效率同单一反应体系趋于一致，副反应基本对系统性能无影响。

关键词: 太阳能, 甲烷, 二氧化碳, 热力学过程, 动态建模, 复杂反应体系

Abstract:

Theoretical analysis of a solar drive methane dry reforming energy storage system was performed based on the first and second laws of thermodynamics, and the energy storage efficiencies of the system with different solar intensity and inlet mole ratios were studied. Species compositions of solar reactor was calculated via equilibrium constant method. Then variation of feed gas conversion, selectivity, work efficiency and energy conversion efficiency under different conditions as well as the influence of side reactions on energy conversion were studied based on the established theoretical model. The results showed that the increase of feed mole ratio of CO₂ to CH₄ could improve the conversion of methane, selectivity, work efficiency and energy conversion efficiency. Reactor temperature would significantly affect the thermochemical storage properties of the system. With lower temperature (923—1123K), more side reactions would happen; and with higher temperature (>1123K), side reactions would be gradually suppressed, leading to less carbon deposition, higher work efficiency and energy conversion efficiency. Work efficiency and energy conversion efficiency reached their peak value at 1123K. After this temperature (>1123K), radiation loss increased significantly, and work efficiency and energy conversion efficiency decreased with the increased temperature. Since sides reactions were obviously suppressed under high temperature region (>1200K), the efficiencies of complex reaction system tended to be consistent with the single reaction system, which meant that the side reaction had no effect on the performances of the whole system.

Key words: solar energy, methane, carbon dioxide, thermodynamics process, dynamic modeling, complex reaction system

中图分类号:

TQ530

徐凯迪,谢涛,王升,杨伯伦. 太阳能甲烷干重整复杂反应体系的热化学储能特性[J]. 化工进展, 2019, 38(11): 4921-4929.

Kaidi XU,Tao XIE,Sheng WANG,Bolun YANG. Thermochemical energy storage characteristics of complex reaction system for solar methane dry reforming system[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4921-4929.

图/表 9

图1 甲烷重整太阳能热化学储能系统

图2 反应器入射太阳辐射强度及太阳辐射能的吸收效率与反应器温度的关系曲线

图3 反应体系的最大理论功和能量转换效率与光照强度的关系曲线

图4 原料气（CH4和CO2）转化率和反应器内的熵变速率与光照强度的关系

图5 不同光照强度下，甲烷和二氧化碳转化率随反应物

图6 不同光照强度下，二氧化碳选择性随反应物进料比

图7 反应器的最大理论功效率和能量转换效率随光照强度、n(CO2)/n(CH4)的变化曲线

图8 在不同反应物进料比下热化学储能密度随光照强度

图9 进料比为1.0时单一反应和复杂反应的功效率和能量

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