폐 RHDS 촉매재생 후 메탈 코로게이트 지지체상에서 워시코팅에 의한 NOx 저감 SCR 촉매에 관한 연구
A Study on the Possibility of Using of Spent RHDS Catalyst as a SCR Catalyst wash-coated on the metal corrugated substrate
RHDS 촉매는 코크와 황 화합물 그리고 금속인 바나듐이 표면에 침적되어 비활성화가 된다. 이러한 오염물을 제거하기 위해서 먼저 폐 RHDS 촉매에 묻어있는 중질유분의 세정, 코크와 황 화합물을 고온 배소 처리한 후, 과량으로 침적되어 있는 바나듐의 침출량을 조절하기 위하여 0.5, 1 wt% 옥살산 수용액을 이용하여 초음파 교반기에서 50 ℃, 10 sec 동안 교반하여 NOx 저감을 위한 SCR 촉매로의 적용 가능성을 확인하고자 하였다. 재생처리 한 RHDS 촉매의 성분은 XRF 를 사용하여 분석하였고, 상압 고정층 연속 흐름 반응기 상에서 NOx 저감 성능을 측정하였다. 옥살산 수용액 0.5 wt%, 10 sec 동안 초음파 침출한 촉매가 가장 안정적인 NOx 저감 성능을 보였으며, 375 ℃ 이상의 고온에서는 상용 촉매와 동등 수준의 NOx 저감 성능을 확인할 수 있었으나 저온영역 200 ℃에서 250 ℃까지는 상용 촉매보다 낮은 NOx 저감 성능을 보였다. 따라서 폐 RHDS 촉매를 재생처리 한 후 분말로 메탈 코로게이트 지지체에 워시코팅한 촉매는 상용 SCR 촉매로서 이용 가능함을 확인하였다.
The spent RHDS (Residue HydroDeSulfurization) catalyst is deactivated mainly by deposition of various contaminants such as coke, sulfur and vanadium on the surface of catalyst. To eliminate those contaminants, the following remanufacturing process was conducted. The first, heavy oil on the surface of the spent RHDS catalyst was removed by kerosene and dehydrated. The second, the high temperature incineration was carried out to eliminate coke and sulfur components deposited on the surface of spent RHDS catalyst. The third, the excessive quantity of Vanadium deposited on the surface of catalyst was removed by leaching process as follows: ultrasonic agitation was carried out at 50℃, for 10 seconds with 0.5% and 1% oxalic acid solution. The purpose of this process is to find out regenerated RHDS catalyst can be used as SCR catalyst for NOx reduction by controlling the vanadium residual content of the regenerated RHDS catalyst through leaching process. The composition of regenerated RHDS catalyst was analyzed by XRF and the NOx reduction efficiency was also measured by continuous catalytic fixed bed reactor. As the result, regenerated catalyst, with 0.5% oxalic acid, ultrasonic agitation in 10 seconds, showed the most stable NOx reduction efficiency. Also, in comparison with commercial SCR catalyst, the NOx reduction performance of regenerated catalyst was similar to that of commercial SCR catalyst at the temperature 375℃ and higher whereas was lower than commercial SCR catalyst at the temperature range between 200∼250℃. Therefore, it was confirmed that the regenerated catalyst as powder form wash coated on the surface of metal corrugated substrate can be used for commercial SCR catalyst.
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