涂覆型蜂窝体催化剂的制备与烟气一氧化碳催化净化性能

刘应书; 张璇; 卞文博; 姜理俊; 刘文海; 侯环宇; 孙方舟; 杨雄; 李子宜

doi:10.13801/j.cnki.fhclxb.20221205.003

涂覆型蜂窝体催化剂的制备与烟气一氧化碳催化净化性能

doi: 10.13801/j.cnki.fhclxb.20221205.003

1.
北京科技大学能源与环境工程学院，北京 100083
2.
河钢集团钢研总院，石家庄 050023

基金项目: 国家自然科学基金(21808012)；河钢集团有限公司重点科技项目(HG2020204-1)

详细信息

通讯作者:
李子宜，博士，教授，博士生导师，研究方向为气体分离与净化　E-mail: ziyili@ustb.edu.cn

中图分类号: TQ426.0；O643.0；TB331
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- 被引次数: 0
出版历程
- 收稿日期: 2022-09-19
- 修回日期: 2022-10-22
- 录用日期: 2022-11-18
- 网络出版日期: 2022-12-05
- 刊出日期: 2023-08-15

Preparation of coated honeycomb catalyst and carbon monoxide catalytic removal of flue gas

1.
School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
Strategic Research Institute of HBIS Group, Shijiazhuang 050023, China

Funds: National Natural Science Foundation of China (21808012); Key Technology Project of HBIS Group CO., LTD. (HG2020204-1)

摘要

摘要: 钢铁烧结烟气CO排放问题日渐被广泛关注，然而当前缺乏面向大流量烟气的高效实用型CO净化技术。将粉末催化剂涂覆到堇青石蜂窝陶瓷载体上制得了一系列涂覆型催化剂，基于系列表征技术分析了涂覆型催化剂的理化特性，并在实际烧结烟气条件下评测了CO催化性能。结果表明：浆液1wt‰聚乙烯醇含量与300℃焙烧可促进粉末催化剂在载体表面分布的均匀性，并提高了Mn⁴⁺/Mn³⁺与O_ads/O_latt比值；优选涂覆型催化剂经过60 min超声后的涂层脱落率为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内保持稳定；在基于某钢厂实际脱硫后的烧结烟气中，720 h后效率可稳定在82%以上。研究可为工业烟气CO净化技术的应用提供参考。
- 涂覆型催化剂 /
- 涂层 /
- 一氧化碳 /
- 蜂窝陶瓷载体 /
- 焙烧温度 /
- 脱落率
Abstract: 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 1wt‰ 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 O_ads/O_latt. The coating shedding rate of the optimized coated catalyst is 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.
- coated catalyst /
- coating /
- carbon monoxide /
- honeycomb ceramic support /
- calcination temperature /
- shedding rate

HTML全文

图 1 催化性能评估测试系统

MFC—Mass flow controller; GC-FID—Flame ionization detector

Figure 1. Catalytic performance evaluation test system

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图 2 粉末与涂覆型催化剂的XRD图谱

Figure 2. XRD patterns of powder and coated catalysts

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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

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图 4 粉末与涂覆型催化剂的Ar吸脱附等温线 (a) 和孔径分布 (b)

Figure 4. Ar adsorption-desorption isotherms (a) and pore-size distribution (b) of powder and coated catalysts

dV/dD—Differential pore volume

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图 5 粉末与涂覆型催化剂的XPS图谱

Figure 5. XPS spectra of powder and coated catalysts

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图 6 粉末与涂覆型催化剂的程序升温还原(H₂-TPR)图谱

Figure 6. Temperature programmed reduction (H₂-TPR) spectra of powder and coated catalysts

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图 7 浆液性质及涂层脱落率

Figure 7. Slurry properties and coating shedding rate

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图 8 CO催化效率及稳定性曲线

Figure 8. CO catalytic efficiency and stability curves

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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

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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 sample	Binding energy/eV					Mn⁴⁺/Mn³⁺	O_ads/O_latt
Number of sample	Mn³⁺2p_3/2	Mn⁴⁺2p_3/2	Cu²⁺2p_3/2	O_ads1s	O_latt1s	Mn⁴⁺/Mn³⁺	O_ads/O_latt
PC	642.0	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

Sample	Slurry polyvinyl alcohol content/wt‰	Calcination temperature/℃	Shedding rate/%
CC¹₃₀₀	1	300	1.25
CC¹₄₀₀	1	400	1.97
CC¹₅₀₀	1	500	3.03
CC⁰₃₀₀	0	300	15.78
CC^0.5₃₀₀	0.5	300	5.67
CC^1.5₃₀₀	1.5	300	3.42

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