| Citation: |
LIU Yingshu, ZHANG Xuan, BIAN Wenbo, et al. Preparation of coated honeycomb catalyst and carbon monoxide catalytic removal of flue gas[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 4539-4548. DOI: 10.13801/j.cnki.fhclxb.20221205.003
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Carbon monoxide (CO), as a common poisonous and harmful gas, is a threat to human life and environment. Industrial waste gas, automobile exhaust, incomplete combustion of fossil fuels and so on emit a lot of CO. The catalytic purification of CO from industrial flue gas is becoming more and more urgent for the high activity durable coating catalyst. The effects of slurry properties and calcination temperature on the coating strength and CO catalytic performance of the coated catalyst in humid atmosphere were explored, and the catalytic purification test for 720 h was carried out based on the selected coated samples under actual sintering flue gas conditions.
A series of coated catalysts were prepared by coating the powder catalyst on cordierite honeycomb ceramic supports. The effects of slurry properties and calcination temperature on the coating strength and the catalytic oxidation activity and stability of the coated catalyst in the aqueous environment were investigated. The catalytic stability of the selected coated catalyst in the actual sintering flue gas was also tested. X-ray powder diffraction, Ar absorption and desorption characteristics, microscopic morphology analysis, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, temperature programmed reduction and other characterization techniques were used to analyze and test the material properties in order to explore the relationship between the coating type catalyst's detachment resistance and CO catalytic oxidation performance and the physical and chemical properties of the material.
The presence of polyvinyl alcohol in the catalyst slurry provides steric hindrance to disperse and prevent the agglomeration of particles, and makes SiO evenly distributed around the catalyst, which improves the dispersion stability of the suspension and produces a uniform and dense coating. The coated catalyst prepared by slurry with 1‰ polyvinyl alcohol addition and calcinated at 300℃ after 60 min ultrasonic treatment has a coating shedding rate of 1.25%, and maintains a high catalytic efficiency during 72h stability test. However, the coated catalyst prepared without polyvinyl alcohol slurry has uneven distribution of active components and poor adhesion. After 60 min of ultrasound, the coating peeling rate was 15.78%, and the efficiency decreased significantly in 72h stability test. The lower calcination temperature can reduce the agglomeration of the catalyst and make the catalyst have a lower reduction temperature and a higher ratio of Mn/Mn to O/O, so that it can catalyze CO efficiently in the water condition for a long time. The optimal coated catalyst efficiency is slightly lower than that of powder catalyst. Considering that the mass space velocity of coated catalyst is much greater than that of powder catalyst at the same volume space velocity, coated catalyst still retains the strong CO catalytic ability of the original powder. The optimized coated catalyst can achieve 99%CO conversion at 7500 h space velocity, 1%CO, 8% water vapor content, 110℃, and remains stable within 72 h. In the sintering flue gas based on the actual desulfurization of a steel plant, the efficiency can be stable at more than 82% after 720 h.Conclusions: The influence law of slurry properties and calcination temperature on coating strength and CO catalytic performance of coated catalyst was explored. A catalyst was selected and its practicability in actual sintering flue gas was verified. It was found that coated catalyst had higher O/O ratio and lower reduction temperature than powder catalyst. The catalyst can be evenly distributed on the cordierite support with appropriate amount of polyvinyl alcohol, which is beneficial to improve the utilization rate of catalyst and make the catalyst not easy to fall off. Higher calcination temperature can promote the agglomeration of catalysts, decrease the specific surface area, reduce the surface active sites, reduce the ratio of Mn/Mn to O/O, reduce the reducing ability of catalysts, and weaken the catalytic activity of CO. The coated catalyst prepared with 1‰ polyvinyl alcohol and calcined at 300℃ has the best coating strength and catalytic activity. For the actual sintering flue gas with space velocity of 6000 h and water vapor volume fraction of 12~15%, the catalytic efficiency can be stabilized above 82% for a long time (>720 h).
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