Zhikai Li

A logic-based controller for the mitigation of ventilation air methane in a catalytic flow reversal reactor

The control system of a catalytic flow reversal reactor (CFRR) for the mitigation of ventilation air methane was investigated. A one-dimensional heterogeneous model with a logic-based controller was applied to simulate the CFRR. The simulation results indicated that the controller developed in this work performs well under normal conditions. Air dilution and auxiliary methane injection are effective to avoid the catalyst overheating and reaction extinction caused by prolonged rich and lean feed conditions, respectively. In contrast, the reactor is prone to lose control by adjusting the switching time solely. Air dilution exhibits the effects of two contradictory aspects on the operation of CFRR, i.e., cooling the bed and accumulating heat, though the former is in general more prominent. Lowering the reference temperature for flow reversal can decrease the bed temperature and benefit stable operation under rich methane feed condition.

Synthesis of Chainlike ZSM-5 Zeolites: Determination of Synthesis Parameters, Mechanism of Chainlike Morphology Formation, and Their Performance in Selective Adsorption of Xylene Isomers

Chainlike zeolites are advantageous to various applications as a catalyst or an adsorbent with specific selectivity; however, it is often very difficult to get desired morphology due to the complexity of zeolite synthesis process. In this work, appropriate parameters for the synthesis of perfect chainlike ZSM-5 zeolites were well determined, which illustrates that the chain length can be controlled by the composition of synthesis mixture, the amount of residual alcohol in the synthesis system, and the crystallization time. Moreover, the mechanism of chainlike crystal growth was investigated by analyzing the surface species during the synthesis process, with the help of density functional theory (DFT) calculation. The results indicate that the formation of disk crystals with proper dimension and flat surface having abundant hydroxyl groups is crucial to the growth of chainlike ZSM-5 crystals; the condensation of Si-OH groups on the (010) facet is energetically more favorable than that on other facets, leading to the growth of MFI crystals along the b-orientation. Through finely tuning the multifarious synthesis parameters, chainlike ZSM-5 zeolites with controllable length in b-orientation are obtained without using any other extra organic additives except the necessary template agent such as tetrapropylammonium hydroxide (TPAOH). Owing to the increased tortuosity of pore channels in the chainlike ZSM-5, the difference between p-xylene and o/m-xylenes in their adsorption behavior and diffusivity is greatly enhanced. These results help to clarify the formation mechanism of zeolites with chainlike morphology and then bring forward an effective approach to get zeolite materials with specific properties in adsorption and catalysis.

Preferential Oxidation of CO in H 2 -Rich Stream Over Au/CeO 2 –NiO Catalysts: Effect of the Preparation Method

AbstractTwo methods, viz., the hydrothermal (HT) and co-precipitation (CP) methods, were used to prepare CeO2–NiO composite oxides; with them as the supports, Au/CeO2–NiO catalysts were prepared by the colloidal deposition method and used in the preferential oxidation (PROX) of CO in H2-rich stream. Various characterization measures such as N2 sorption, XRD, TEM, H2-TPR, Raman spectroscopy and XPS were used to clarify the influence of preparation method on the structure of CeO2–NiO support and the performance of Au/CeO2–NiO catalyst. The XPS and TEM results reveal that the CeO2–NiO(HT) support prepared by hydrothermal method displays a uniform rod-like shape and exposes preferentially the (110) and (100) planes of CeO2, whereas the CeO2–NiO(CP) support prepared by co-precipitation method is composed of nanorods and irregular nanoparticles dominated by (111) facets of CeO2. After deposition of gold, both the Au/CeO2–NiO(HT) and Au/CeO2–NiO(CP) catalysts are alike in the state and size distribution of deposited Au nanoparticles. The H2-TPR results indicate that the presence of Au strongly promotes the reduction of CeO2 in the Au/CeO2–NiO catalyst. Raman spectra illustrate that the incorporation of Ni ions into CeO2 remarkably increases the amount of oxygen vacancies in the CeO2–NiO supports, especially in CeO2–NiO(HT) prepared by hydrothermal method, which is beneficial to the dispersion and stabilization of gold species. The structure of CeO2–NiO support and catalytic activity of Au/CeO2–NiO in CO PROX is strongly related to the preparation method; Au/CeO2–NiO(HT) exhibits much higher activity than Au/CeO2–NiO(CP). The larger fraction of (110) and (100) CeO2 facets in CeO2–NiO(HT) can promote the dispersion of gold species, formation of oxygen vacancies and migration of oxygen species, which are effective to enhance the redox capacity and activity of the obtained Au/CeO2–NiO(HT) catalyst for CO PROX in H2-rich stream.Graphical AbstractAu supported on CeO2–NiO nanorods prepared by hydrothermal method exhibits much higher catalytic activity for CO PROX in H2-rich stream.