CaSO4氧载体与CO反应中Boudouard反应的热力学分析及其抑制研究

化工进展

CaSO4氧载体与CO反应中Boudouard反应的热力学分析及其抑制研究

郑敏1，沈来宏2

1昆明理工大学冶金节能减排教育部工程研究中心，云南昆明 650093；2东南大学能源与环境学院，江苏南京 210096

出版日期:2013-12-05 发布日期:2013-12-04

Thermodynamic analysis and suppress research on the Boudouard reaction in the reaction of CaSO4 oxygen carrier with CO

ZHENG Min1，SHEN Laihong2

1Engineering Research Center of Metallurgical Energy Conservation and Emission Reduction，Ministry of Education，Kunming University of Science and Technology，Kunming 650093，Yunnan，China；2School of Energy & Environment，Southeast University，Nanjing 210096，Jiangsu，China

Online:2013-12-05 Published:2013-12-04

摘要/Abstract

摘要： 在反应温度500～1200 ℃、CO浓度0.5%～99.0%、CO2浓度0～70%和SO2浓度0～10%条件下，利用化学平衡常数，对化学链燃烧 CaSO4与CO反应过程中Boudouard反应的可行性展开热力学研究，获得了抑制Boudouard反应及积碳生成的方法。由于CaSO4竞争还原反应和Boudouard反应平衡常数的表达形式不同，通过比较各个反应的CO平衡转化率以判断各个反应进行程度的高低。在化学链燃烧燃料反应器适宜温度范围（850～1050 ℃），CO浓度越高，Boudouard反应越容易进行，SO2浓度对Boudouard反应进行的程度没有影响。而提高反应温度和反应气中CO2浓度，则有利于抑制Boudouard反应的进行。当气体反应物中CO2浓度超过3.7%，即使CO浓度达到95.0%，Boudouard反应不能进行。

关键词: 化学链燃烧, CaSO4竞争还原反应, Boudouard反应, 积碳

Abstract: For the application of CaSO4 oxygen carrier in chemical looping combustion (CLC)，the thermodynamic of Boudouard reaction during the process of CaSO4 reduction with CO were investigated at 500—1200 ℃，at different CO concentrations (0.5%—99.0%)，CO2 concentrations (0—70%) and SO2 concentrations (0—10%). And the control method of the Boudouard reaction for less carbon deposition on oxygen carrier was discussed. The expression forms of the equilibrium constants of CaSO4 reductions and Boudouard reaction differed，and therefore，direct comparisons on the extents of the chemical reactions cannot be done. The extents of the chemical reactions of the competitive reductions of CaSO4 and the side reaction of the Boudouard reaction were analyzed based on the CO equilibrium conversions. For the suitable temperature of fuel reactor in CLC (850—1050 ℃)，higher CO concentrations favor the Boudouard reaction，while the SO2 concentrations had no effects on the extent of the Boudouard reaction. The Boudouard reaction was suppressed at higher reaction temperatures and higher CO2 concentrations. Furthermore，when the CO concentration was at 95% and the CO2 concentration in the gas reactant was above 3.7%，the Boudouard reaction was not able to be initiated.

Key words: chemical looping combustion, competitive reduction of CaSO4, Boudouard reaction, carbon deposition

郑敏1，沈来宏2. CaSO4氧载体与CO反应中Boudouard反应的热力学分析及其抑制研究[J]. 化工进展.

ZHENG Min1，SHEN Laihong2. Thermodynamic analysis and suppress research on the Boudouard reaction in the reaction of CaSO4 oxygen carrier with CO[J]. Chemical Industry and Engineering Progree.

[1]	袁妮妮, 郭拓, 白红存, 何育荣, 袁永宁, 马晶晶, 郭庆杰. 化学链燃烧过程Fe₂O₃/Al₂O₃载氧体表面CH₄反应：ReaxFF-MD模拟[J]. 化工学报, 2022, 73(9): 4054-4061.
[2]	武永健, 罗春欢, 魏琳, 朱探金, 苏庆泉. 基于化学链燃烧的转炉放散煤气利用研究[J]. 化工学报, 2019, 70(5): 1923-1931.
[3]	闫景春, 沈来宏, 蒋守席, 葛晖骏. 高钠煤化学链燃烧特性及煤焦气化反应动力学研究[J]. 化工学报, 2019, 70(5): 1913-1922.
[4]	殷上轶, 宋涛. CO₂气氛下准东煤化学链燃烧特性研究[J]. 化工学报, 2018, 69(9): 3954-3964.
[5]	张志丰, 王亦飞, 朱龙雏, 李季林, 王辅臣, 于广锁. 基于铁基载氧体的无烟煤化学链燃烧过程中硫分布特性[J]. 化工学报, 2018, 69(4): 1578-1585.
[6]	彭松, 曾德望, 陈超, 邱宇, 肖睿. 具有自载体功能的CoFeAlO₄载氧体化学链燃烧反应特性[J]. 化工学报, 2018, 69(1): 515-522.
[7]	戴金鑫, 刘晶, 刘丰. 化学链燃烧中H₂S对NiFe₂O₄氧载体活性的影响机理[J]. 化工学报, 2017, 68(3): 1163-1169.
[8]	覃吴, 侯翠翠, 张俊姣, 肖显斌, 程伟良, 董长青, 杨勇平. Co-Fe₂O₃[104]铁基载氧体优化体系作用下褐煤化学链燃烧特性[J]. 化工学报, 2016, 67(4): 1459-1466.
[9]	肖申, 沈来宏, 牛欣, 顾海明, 葛晖骏. 含氮模型化合物用于化学链燃烧的氮氧化物释放特性[J]. 化工学报, 2015, 66(11): 4588-4596.
[10]	覃吴, 李渠, 董长青, 程伟良, 杨勇平. Co-Fe₂O₃纳米载氧体作用下CO化学链燃烧富集CO₂[J]. 化工学报, 2014, 65(8): 3136-3143.
[11]	许迪恺, Tong Andrew, 曾亮, 罗四维, 范良士. 铁基移动床化学链技术进展[J]. CIESC Journal, 2014, 65(7): 2410-2416.
[12]	张思文, 沈来宏, 顾海明, 刘卫东, 葛晖俊. 钠修饰铁矿石载氧体的串行流化床煤化学链燃烧试验[J]. 化工学报, 2013, 64(11): 4187-4195.
[13]	张思文1，吴家桦2，顾海明1，沈来宏1，肖军1. 串行流化床内气体串混特性[J]. 化工学报, 2012, 63(7): 2017-2024.
[14]	玄伟伟，张建胜. 化学链燃烧铁基载氧体还原反应积炭趋势[J]. 化工学报, 2012, 63(3): 904-909.
[15]	石司默, 董长青, 覃吴, 王磊, 李文艳, 杨勇平. Fe₂O₃/粉煤灰载氧体化学链燃烧实验与机理研究[J]. 化工学报, 2012, 63(12): 4010-4018.