Preparation of coated honeycomb catalyst and carbon monoxide catalytic removal of flue gas
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摘要:
工业烟气一氧化碳(CO)的催化净化对高活性耐久涂覆型催化剂的需求日渐迫切。涂覆型催化剂的实际应用可能伴随着快速的烟气流动、剧烈的温度波动和强烈的机械振动，催化剂脱落会造成阀门及后端设备堵塞，并导致催化效率衰减，而且传统商用铜锰催化剂在含水环境中容易失活。上述问题很大程度限制了烧结烟气CO催化净化技术的推广应用。本文将多元金属氧化物催化剂配置成浆液并涂覆到堇青石蜂窝陶瓷载体上制得了一种陶瓷基复合材料(多元金属/堇青石涂覆型催化剂)。浆液中聚乙烯醇的存在提供了空间位阻，以分散颗粒和阻碍颗粒团聚，并使SiO2在催化剂周围均匀分布，提高了悬浮液的分散稳定性，制备出了均匀致密的涂层。较低的焙烧温度能减少催化剂团聚并使催化剂具有较低的还原温度、较高的Mn4+/Mn3+与Oads/Olatt比值，使其在含水条件中能长期高效催化CO。优选涂覆型催化剂经过60 min超声后的涂层脱落率仅为1.25%；在7500 h-1空速、1%CO、8%水蒸气含量、110℃下可达到99%CO转化率，并在72 h的稳定性测试内保持高催化效率；在基于某钢厂实际脱硫后的烧结烟气中，720 h后催化效率可稳定在82%以上。 CO催化效率及稳定性曲线 Abstract: Carbon monoxide (CO) emission from iron and steel sintering flue gas has been paid more and more attention. However, there is a lack of efficient and practical CO removal technology for large flow flue gas. A series of coated catalysts were prepared by coating powder catalyst on cordierite honeycomb ceramic supports. The physicochemical properties of the coated catalysts were analyzed based on a series of characterization techniques, and the catalytic performance of CO was evaluated under actual sintering flue gas conditions. The results show that 1‰ polyvinyl alcohol content of slurry and 300℃ calcination could promote the uniformity of powder catalyst distribution on the surface of the support, and improve the ratio of Mn4+/Mn3+and Oads/Olatt; The coating shedding rate of the optimized coated catalyst was 1.25% after 60 min ultrasonic vibration; The catalytic efficiency of 99% CO can be achieved at 7500 h−1 space speed, 1%CO, 8% water vapour content and 110℃, and remains stable within 72 h ;Based on the actual desulfurization of sintering flue gas in a steel plant, the efficiency can be stable above 82% after 720 h. The study can provide reference for the application of CO removal technology for industrial flue gas.-
Key words:
- coated catalyst /
- coating /
- carbon monoxide /
- honeycomb ceramic support /
- calcination temperature /
- shedding rate
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图 3 浆液的照片与SEM图像和涂覆型催化剂的SEM及EDS图像
Figure 3. Photos and SEM images of slurries and SEM and EDS images of coated catalysts
图 4 粉末与涂覆型催化剂的Ar吸脱附等温线和孔径分布
Figure 4. Ar adsorption-desorption isotherms and pore-size distribution of powder and coated catalysts
图 9 CC1300的现场CO催化效率稳定性曲线
Figure 9. Stability curve of in-situ CO catalytic efficiency of CC1300
表 1 粉末与涂覆型催化剂的XPS参数
Table 1. XPS parameters of powder and coated catalysts
Number of samples Binding energy/eV Mn4+/Mn3+ Oads/Olatt Mn3+
2 p3/2Mn4+
2 p3/2Cu2+
2 p3/2Oads
1 sOlatt
1 sPC 642 643.8 933.6 531.4 529.6 0.60 0.80 CC1300 641.9 643.9 933.9 532.6 529.6 0.43 3.81 CC1400 641.9 644.0 933.5 532.8 529.8 0.38 3.01 CC1500 641.8 643.8 933.5 532.8 529.8 0.32 2.79 CC0300 641.8 643.9 933.7 532.8 529.6 0.43 3.25 CC1300* 642.5 643.8 934.4 532.8 529.6 0.82 3.17 
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表 2 涂覆型催化剂的涂层脱落率
Table 2. Coating shedding rate of coated catalyst
Samples Slurry polyvinyl
alcohol content/‰Calcination temperature/℃ Sheddin-g rate/% CC1300 1 300 1.25 CC1400 1 400 1.97 CC1500 1 500 3.03 CC0300 0 300 15.78 CC0.5300 0.5 300 5.67 CC1.5300 1.5 300 3.42
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