CO is a toxic gas discharged as a byproduct in tail gases from different industrial flue gases, which needs to be taken care of urgently. In this study, a CuCl/AC adsorbent was made by a facile route of physically mixing CuCl2 and Cu(HCOO)2 powder with activated carbon (AC), followed by heating at 533 K under vacuum. The samples were characterized by X-ray powder diffraction (XRD), inductively coupled plasma optical emission spectrometry (ICP-OES), N2 adsorption/desorption, and scanning electron microscopy (SEM). It was shown that Cu(II) can be completely reduced to Cu(I), and the monolayer dispersion threshold of CuCl on AC support is 4 mmol·g−1 AC. The adsorption isotherms of CO, CO2, CH4, and N2 on CuCl/AC adsorbents were measured by the volumetric method, and the CO/CO2, CO/CH4, and CO/N2 selectivities of the adsorbents were predicted using ideal adsorbed solution theory (IAST). The obtained adsorbent displayed a high CO adsorption capacity, high CO/N2, CO/CH4, and CO/CO2 selectivities, excellent ad/desorption cycle performance, rapid adsorption rate, and appropriate isosteric heat of adsorption, which made it a promising adsorbent for CO separation and purification.
A mesoporous beta zeolite was hydrothermally prepared directly by silanizing silica without any mesoporous template via the bond-blocking principle. Si–C bond-blocking arose during the crystalline growth. The crystallization took more than 10 days, but the material had a fairly stable structure and could even be processed up to 32 days later in the hydrothermal system. XRD, N2-adsorption/desorption and TEM/SEM characterization of the materials indicated that the beta zeolite is truly a sponge-like mesoporous zeolite with a BEA topological structure, which consists of self-sustaining macroscopic sized zeolitic aggregates assembled from nanosized crystalline domains of beta zeolite with intracrystalline mesopores. The mesoporous beta zeolite possessed an extremely large external surface area and adjustable mesoporosity. Compared to conventional beta zeolite, FTIR results of pyridine (Py) and 2,6-di-tert-butylpyridine (DTBPy) demonstrated an increase of the Lewis-site contribution and a large improvement for the accessibility of bulky molecules in the mesoporous beta zeolite. Finally the mesoporous beta zeolite exhibited significant activity in the transesterification reaction of triolein to afford methyl oleate (biodiesel) due to the accessibility increase and diffusion-limitation reduction of large lipids to acid sites in the H-beta zeolite framework.
To improve the catalytic performance of zeolite catalysts in reactions involving bulky molecules, a series of mesoporous Beta zeolite were prepared using organic functionalized fumed silica as the silicon source, which were thoroughly characterized in terms of porosity and acidity. The peaks in X-ray diffraction (XRD) patterns showed broadening, and the external surface area and mesoporosity increased progressively when the content of organic functionalization increased. An infrared (IR) spectroscopy study of adsorbed probe molecules, including pyridine (Py-IR), 2,6-ditertbutylpyridine (DTBPy-IR) and pivalonitrile (Pn-IR), showed that the improvement of mesoporosity increased the accessibility of acidic sites. In the catalytic benzylation of naphthalene with benzyl chloride (BC) over the mesoporous Beta zeolite catalysts, the conversion of BC was significantly increased when the accessibility of Brönsted acid sites improved. The increase of mesoporosity not only improved the diffusion ability of the reactants and products, but also increased the accessibility of acid sites, which greatly enhanced the activity of the mesoporous Beta zeolite catalysts. It is highlighted that the interdependence of mesoporosity, acid type, acid concentration, and strength of the mesoporous Beta zeolites on the catalytic performance in the benzylation of naphthalene with BC was comprehensively studied.
A series of zeolite X/activated carbon (AC) composites were prepared from the same starting materials at various activation time. The corresponding modified samples were obtained by being treated with diluted NH4Cl solution. The relationship between porosity development, surface properties, and CH4/N2 adsorption performance was investigated. The increase of micropore volume is beneficial to the improvement of CH4 and N2 adsorption capacity, but more sensitive for CH4. In addition, the polar functional groups of zeolite X/AC composites may enhance CH4 adsorption capacity. More importantly, both developing micropore structure and surface modification contributed to enhance the adsorption selectivity . As the optimum sample of these studies, HZAC(24) showed CH4 adsorption capacity of 17.3 cm3/g and the highest adsorption selectivity of 3.4. The CH4 and N2 adsorption isotherms of all samples can be well fitted by the Langmuir–Freundlich model. HZAC(24) showed an excellent cyclability of adsorption/desorption of CH4 with a neglectable capacity loss after subsequent cycles. Moreover, HZAC(24) displayed relatively rapid adsorption kinetics. These properties of zeolite X/AC composites are essential for the adsorptive separation of CH4 from N2 in the pressure swing adsorption (PSA) process.