化工学报 ›› 2018, Vol. 69 ›› Issue (5): 2149-2157.DOI: 10.11949/j.issn.0438-1157.20171167

• 能源和环境工程 • 上一篇    下一篇

同时煅烧硫化反应中石灰石微观孔结构演变特性

王子铭, 陈亮, 岳爽, 王春波   

  1. 华北电力大学能源动力与机械工程学院, 河北 保定 071003
  • 收稿日期:2017-08-24 修回日期:2018-01-08 出版日期:2018-05-05 发布日期:2018-05-05
  • 通讯作者: 王春波
  • 基金资助:

    国家重点研发计划项目(2016YFB0600701)。

Microstructure evolution of procedural products during limestone simultaneous calcination/sulfation

WANG Ziming, CHEN Liang, YUE Shuang, WANG Chunbo   

  1. School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, Hebei, China
  • Received:2017-08-24 Revised:2018-01-08 Online:2018-05-05 Published:2018-05-05
  • Supported by:

    supported by the National Key R&D Program of China (2016YFB0600701).

摘要:

采用自制恒温热重实验装置,测试了石灰石同时煅烧硫化反应的煅烧动力学特性和颗粒孔结构演变特性,探讨了孔结构演变机理。当煅烧环境中存在SO2时,石灰石颗粒煅烧的同时发生硫化反应。煅烧环境中SO2的存在降低了石灰石煅烧速率。与纯煅烧相比,同时煅烧硫化反应的比表面积和比孔容增长均较慢,比表面积和比孔容分布曲线均较低,且在反应后期直径2~8 nm内小孔的比表面积和比孔容随时间降低。提出了描述石灰石同时煅烧硫化反应过程中微观孔结构演变的模型:石灰石颗粒的煅烧由颗粒的表面向内进行,在煅烧前期(0~75 s),少量CaSO4在CaO表面生成,小部分孔隙被CaSO4堵塞,CaSO4对煅烧速率和孔结构的影响较小;在煅烧中期(75~225 s),CaSO4厚度和覆盖面积不断增加,堵塞孔体积增加,CO2的扩散阻力增加,导致石灰石的煅烧速率下降;煅烧后期(225~300 s),由于CaSO4的不断积累,孔隙堵塞加剧,且堵塞主要发生在小孔上。对煅烧过程堵塞孔体积的计算表明,在煅烧前期和中期孔堵塞现象已经发生,在反应后期孔堵塞体积快速增加。

关键词: 循环流化床, 反应动力学, 模型, 煅烧, 硫化

Abstract:

The calcination kinetics and pore structure evolution of limestone in simultaneous calcination/sulfation was studied by a self-designed constant-temperature thermogravimetric reactor. Sulfation reaction took place to form CaSO4 simultaneously with limestone calcination as long as SO2 gas was present. The presence of SO2 reduced calcination rate of limestone. Compared to pure calcination, simultaneous calcination/sulfation had slower increase in specific surface area and specific pore volume, which both distribution curves were lower, and these two parameters of small pores with 2-8 nm in diameters decreased with time in the final calcination stage. A mechanism was proposed to describe pore microstructure evolution during simultaneous calcination and sulfation, that is, because limestone calcination occurs from surface to inner core, small amount of CaSO4 was formed on CaO surface with few plugged pores and CaSO4 had little effect on calcination rate and pore structure in initial reaction stage (0-75 s), continuous increase of CaSO4 thickness and coverage enlarged both volume of closed pore and CO2 diffusion resistance but declined calcination rate in the middle calcination stage (75-225 s), and further accumulation of CaSO4 accelerated plugging on pores especially smaller ones in the final stage (225-300 s). Calculation of volume of closed pores showed that pore plugging started in initial and middle calcination stages and intensified rapidly in final reaction stage, which validated the proposed mechanism.

Key words: circulating fluidized bed, reaction kinetics, model, calcination, sulfation

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