Hong Phuong Phan, Cam Anh Ha, Tri Nguyen, Phung Anh Nguyen, Cam Loc Luu
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology (HCMUT), 268 Ly Thuong Kiet Street, Ho Chi Minh City 701000, Vietnam.
Vietnam National University Ho Chi Minh City, Linh Trung Ward, Thu Duc District, Ho Chi Minh City 701000, Vietnam.
ACS Omega. 2022 Jun 2;7(23):20092-20103. doi: 10.1021/acsomega.2c01931. eCollection 2022 Jun 14.
Ni-based catalysts dispersed on different supports (MgO-α-AlO, CeO, SBA-15, and MgO-SBA-15) were prepared by the impregnation method. Characteristics of the catalysts, including specific surface areas (N physisorption), crystalline phase compositions (powder X-ray diffraction, Raman spectroscopy), reducibility (hydrogen temperature-programmed reduction, H-TPR), and morphology (scanning electron microscopy (SEM) and transmission electron microscopy, TEM)) were investigated. The activity and stability of the catalysts were tested for the combined steam and CO reforming of methane at 700 °C in a microflow system. The results show that the catalysts exhibit high activity in the BRM reaction. At 700 °C, the conversion of CH and CO reached 86-99% and 67-80%, respectively, in which the Ni/Mg-SBA catalyst is the best with conversions of CH and CO reaching 99% and 80%. Coke accumulation on the surface of the catalysts for 100 h time on stream (TOS) was evaluated by the temperature-programmed oxidation (TPO) technique. The major cause of the catalytic deactivation was elucidated by combining the determination of the amount and type of deposited coke with the changes in the physicochemical properties of the catalysts after the long-term reaction. Almost complete loss of activity was observed on Ni/Mg-Al catalyst after 100 h TOS, while the activity drop was slow on the Ni/Mg-SBA sample, about 15-20% of the total value. Otherwise, the Ni/CeO and Ni/SBA catalysts firmly retained their stable activity for 100 h TOS due to the minimal carbon deposition and stability of these catalysts' structure. The highly considerable formation of inert C carbon and sintering over Ni catalyst supported on MgO-α-AlO were responsible for the lower stability of this catalyst compared to those supported on CeO and SBA-15.
采用浸渍法制备了负载在不同载体(MgO-α-AlO、CeO、SBA-15和MgO-SBA-15)上的镍基催化剂。研究了催化剂的特性,包括比表面积(物理吸附法)、晶相组成(粉末X射线衍射、拉曼光谱)、还原性(氢气程序升温还原,H-TPR)以及形貌(扫描电子显微镜(SEM)和透射电子显微镜,TEM))。在微流系统中于700℃下对催化剂进行了甲烷水蒸气重整和CO重整的活性及稳定性测试。结果表明,催化剂在BRM反应中表现出高活性。在700℃时,CH和CO的转化率分别达到86-99%和67-80%,其中Ni/Mg-SBA催化剂最佳,CH和CO的转化率分别达到99%和80%。通过程序升温氧化(TPO)技术评估了催化剂在100小时连续运行时间(TOS)内表面的积炭情况。通过将沉积焦炭的量和类型的测定与长期反应后催化剂物理化学性质的变化相结合,阐明了催化失活的主要原因。在100小时TOS后,Ni/Mg-Al催化剂几乎完全失去活性,而Ni/Mg-SBA样品的活性下降缓慢,约为总值的15-20%。此外,Ni/CeO和Ni/SBA催化剂在100小时TOS内由于碳沉积最少且结构稳定而牢固地保持了其稳定活性。与负载在CeO和SBA-15上的催化剂相比,负载在MgO-α-AlO上的Ni催化剂上大量生成惰性C碳和烧结是导致该催化剂稳定性较低的原因。