石灰石煅烧与硫化条件下磨耗特性

doi:10.11949/0438-1157.20190335

摘要/Abstract

摘要：

石灰石磨耗特性对于循环流化床物料平衡和脱硫效率有重要影响。利用鼓泡床磨耗实验台，系统地研究了不同煅烧与硫化条件下，粒径、温度和SO₂浓度对石灰石及其脱硫产物的磨耗速率的影响。实验结果表明，硫化反应会显著降低石灰石的磨耗速率，延迟到达稳定磨耗的时间；当硫化反应达到慢反应区时，脱硫产物磨耗速率趋于稳定。磨耗可以剥离颗粒表层CaSO₄，从而提高脱硫剂转化率。相同反应条件下，脱硫产物钙转化率越高，石灰石磨耗速率越低。最后利用现有文献数据分析并验证了石灰石磨耗模型，能够较好地反映不同粒径石灰石的磨耗速率的差异。

关键词: 流化床, 模型, 石灰石, 化学反应, 磨耗, 二氧化硫

Abstract:

Attrition characteristics of limestone has a significant effect on material balance and SO₂ capture efficiency in circulating fluidized beds. A bubbling reactor system, equipped with a particle separation apparatus and mass spectrum analyzer, was used to investigate the mutual influence between the calcination and sulfation reactions and the limestone attrition under different conditions. The results showed that sulfation reaction would be significantly reduced the attrition rate, delaying the time for reaching to the stable attrition rate. As the sulfation reaction progressed, the outer surface layer of a CaO particle was gradually covered by CaSO₄. After the initial fast reaction finished, the attrition rates of limestone tended to be stable. Attrition would remove the impervious sulfate layers and enhance the sulfation conversion. Besides, the attrition rate decreased with the increasing sulfation conversion at the same reaction condition. Finally, using the existing literature data to analyze and verify the limestone attrition model, it can better reflect the difference in attrition rate of limestone with different particle sizes.

Key words: fluidized bed, model, limestone, chemical reaction, attrition, sulfur dioxide

中图分类号:

X 701.3

蔡润夏, 黄逸群, 程璐, 李东方, 杨海瑞, 吕俊复, 张缦. 石灰石煅烧与硫化条件下磨耗特性[J]. 化工学报, 2019, 70(8): 3086-3093.

Runxia CAI, Yiqun HUANG, Lu CHENG, Dongfang LI, Chung-hwan JEON, Hairui YANG, Junfu LYU, Man ZHANG. Attrition of limestone during fluidized bed calcination and sulfation[J]. CIESC Journal, 2019, 70(8): 3086-3093.

图/表 13

图1 石灰石磨耗特性实验系统

Fig.1 Experimental apparatus for attritions of limestone

图2 石英砂床料粒径分布

Fig.2 Particle size distribution of silica sand

表1 石灰石磨耗实验关键变量

Table 1 Experimental parameters of attritions of limestone

变量	参数
温度 /℃	800,850,900
SO₂浓度φ(SO₂) /%	0.1, 0.2
粒径(d ₅₀/d ₃₂)/μm	346.2/320.4,609.7/586.4
反应条件	仅煅烧不硫化，先煅烧后硫化，同时煅烧和硫化

图3 脱硫过程对石灰石磨耗速率的影响（320 μm，φ(SO2)=0.2%）

Fig.3 Time variation of attrition rate of lime and its sulfide product (320 μm, φ(SO2)=0.2%)

图4 同时煅烧与硫化条件下SO2和CO2浓度变化（320 μm）

Fig.4 Time variation of SO2 and CO2 under simultaneous calcination and sulfation (320 μm)

图5 不同煅烧条件下石灰石脱硫转化率随时间的变化（320 μm, φ(SO2)=0.2%）

Fig.5 Sulfation conversion versus time under different calcination conditions (320 μm, φ(SO2)=0.2%)

图6 不同时间磨耗产物S元素能谱分析（同时煅烧和硫化，320 μm, φ(SO2)=0.2%）

Fig.6 Energy spectrum analysis (EDS) of sulfur element of attrition particles at different time (simultaneous calcination and sulfation, 320 μm, φ(SO2)=0.2%)

图7 SO2浓度对石灰石磨耗速率的影响（同时煅烧和硫化，320 μm）

Fig.7 Effects of SO2 concentration on attrition rate (simultaneous calcination and sulfation, 320 μm)

图8 SO2浓度对石灰石脱硫转化率的影响（同时煅烧和硫化，320 μm）

Fig.8 Effects of SO2 concentration on sulfation conversion (simultaneous calcination and sulfation, 320 μm)

图9 温度对石灰石磨耗速率的影响（同时煅烧和硫化，320 μm，φ(SO2)=0.2%）

Fig.9 Effects of temperature on attrition rate (simultaneous calcination and sulfation, 320 μm, φ(SO2)=0.2%)

图10 粒径对石灰石磨耗速率的影响（同时煅烧和硫化，850℃，φ(SO2)=0.2%）

Fig.10 Effects of particle size on attrition rate (simultaneous calcination and sulfation, 850℃, φ(SO2)=0.2%)

图11 粒径对石灰石脱硫转化率的影响（同时煅烧和硫化，850℃，φ(SO2)=0.2%）

Fig.11 Effects of particle size on sulfation conversion (simultaneous calcination and sulfation, 850℃，φ(SO2)=0.2%)

图12 不同粒径石灰石磨耗速率常数预测结果

Fig.12 Prediction of attrition rate constant of limestones with different particle sizes

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