Metal–Organic Framework Materials for Desulfurization by Adsorption

Abstract

Current European regulations limit the sulfur content of gasoline to 10 ppmw. Such deep desulfurization levels can be achieved by catalytic hydrodesulfurization processes, but they are accompanied by excessive H2 consumption for unwanted side reactions, in particular, for the hydrogenation of olefins. Selective adsorption constitutes an attractive alternative to catalytic desulfurization. The main challenge is to find adsorbents able to remove the sulfur compounds with very high selectivity from a complex mixture of paraffins, naphthenes, olefins, and aromatic compounds. In the present contribution we present the screening of a large number of metal–organic frameworks (MOFs) for this purpose, using batch adsorption experiments. For the two most promising structures (HKUST-1 and CPO-27-Ni, two cus-MOFs, that is, with coordinatively unsaturated sites), the dynamic behavior, the impact of a model nitrogen-containing compound (pyridine) on the adsorption properties, as well as the regenerability were also evaluated by breakthrough experiments. The good results obtained in purification of our model feeds incited us to perform measurements with a real gasoline feed using batch measurements. The feasibility of adsorptive desulfurization of gasoline using MOFs is discussed on the basis of these results.

Generation of Defect‐Modulated Metal–Organic Frameworks by Fragmented‐Linker Co‐Assembly of CPO‐27(M) Frameworks

“…After the doping of BDC‐OH into the Mg II /DOBDC frameworks, the formed materials were made of agglomerated shuttlelike or needle‐type crystals shaped similarly to cauliflowers (Figure 8), in accordance with the previous reports on Mg II /DOBDC 21–23. Similarly, after 30 % substitution of BDC‐OH into the Ni II /DOBDC frameworks, the formed materials showed agglomerated needlelike shapes similar to cauliflower shapes (Figure 9) and identical to the reported structure for Ni II /DOBDC 21,24. After 30 % incorporation of BDC‐OH into the Co II /DOBDC framework, the formed materials showed a hexagonal column structure (Figure 10), the same structure as that reported for Co II /DOBDC 21,25,26…”

Water Purification: Adsorption over Metal‐Organic Frameworks

“…low capacity, weak interaction and hardship in regeneration) for contaminant removal in water purification. [40][41][42][43][44][45][46][47][48] During past decades, their applications for water purifications have been widely investigated. Therefore, superior adsorbents with large number of active sites and higher surface areas might be desirable to get a better access to qualified water in a reliable, efficient, convenient and low cost way.…”

Adsorption of N/S heterocycles in the flexible metal–organic framework MIL-53(FeIII) studied by in situ energy dispersive X-ray diffraction

“…Maes et al have shown that MOFs like the Fe-trimesate MIL-100(Fe) or the Cu-trimesate Cu-BTC are capable of removing the nitrogen or sulfur compounds from a N/S-contaminated fuel. 7,[12][13][14][15][16][17] Using coordinatively unsaturated metal sites increases the heat of adsorption, 18 and therefore the energy input required for desorption of adsorbed molecules. 7,[12][13][14][15][16][17] Using coordinatively unsaturated metal sites increases the heat of adsorption, 18 and therefore the energy input required for desorption of adsorbed molecules.…”