Selective Production of Phenol on Bifunctional, Hierarchical ZSM-5 Zeolites

Mono- and bimetallic Ni-, Ru- and Pt-modified hierarchical ZSM-5 materials were prepared by impregnation technique and characterized by X-ray diffraction (XRD), N2 physisorption, temperature-programmed reduction (TPR–TGA), ATR–FTIR and solid state NMR spectroscopy. Formation of finely dispersed nickel, ruthenium and platinum species was observed on the bimetallic catalysts. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides and their dispersion and reducibility. The samples’ acidity was studied via FTIR spectroscopy of adsorbed pyridine. The changes in the zeolite structure were studied via solid-state NMR spectroscopy. The catalysts were investigated in a gas-phase hydrodeoxygenation, transalkylation and dealkylation reaction of model lignin derivative molecules for phenol production.

Ring Enlargement of Methylcyclopentane over Pt/(HZSM-48+pseudoboehmite) Catalysts

Platinum catalysts loaded on a hybrid support, composed of HZSM-48 and pseudoboehmite, were applied to the synthesis of benzene through methylcyclopentane (MCP) reforming in order to investigate the effect of the addition of pseudoboehmite to Pt/HZSM-48 for ring-enlargement reaction. A total of 0.5 wt% of platinum was impregnated on the hybrid support by using the incipient wetness method. Catalyst characterization was performed with nitrogen sorption, X-ray diffraction, temperature-programmed desorption of NH3, and infrared spectroscopy of adsorbed pyridine. It was found that mesoporous structures were well-developed in Pt/(HZSM-48 + pseudoboehmite) catalyst as a result of the pseudoboehmite addition, of which the average pore size was in the range of 7–8 nm. The presence of pseudoboehmite in the catalyst increases the total amount of acid sites and weakens the acid strength, compared with those of the Pt/HZSM-48 catalyst. Lewis acid sites were more abundant than Brönsted acid sites over the Pt/(HZSM-48+pseudoboehmite) catalysts. It was found that selectivity to the ring-enlargement reaction is dominant over selectivity to the ring-opening reaction over the Pt/(HZSM-48 + pseudoboehmite) catalysts. The benzene yield over Pt/(HZSM-48 + pseudoboehmite, 1:1) catalyst reached 65.1% at 450 °C and 0.3 h−1. As well as being influenced by the mesoporous structure, the higher activity and selectivity in MCP reforming was also determined by appropriate acidity of the Pt/(HZSM-48 + pseudoboehmite) catalysts.

MPV Reduction of Furfural to Furfuryl Alcohol on Mg, Zr, Ti, Zr–Ti, and Mg–Ti Solids: Influence of Acid–Base Properties

The Meerwein–Ponndorf–Verley (MPV) reaction is an environmentally-friendly process consisting of the reduction of a carbonyl compound through hydrogen transfer from a secondary alcohol. This work deals with MPV reduction of furfural to furfuryl alcohol on different ZrOx, MgOx, TiOx, and Mg–Ti, as well as Zr–Ti mixed systems. The solids were synthesized through the sol–gel process and subsequently calcined at 200 °C. Characterization was performed using a wide range of techniques: ICP-MS, N2 adsorption-desorption isotherms, EDX, TGA-DTA, XRD, XPS, TEM, TPD of pre-adsorbed pyridine (acidity) and CO2 (basicity), DRIFT of adsorbed pyridine, and methylbutynol (MBOH) test reaction. ZrOx showed the highest conversion and selectivity values, which was attributed to the existence of acid–base pair sites (as evidenced by the MBOH test reaction), whereas the introduction of titanium resulted in the drop of both conversion and selectivity probably due to the increase in Brönsted-type acidity. As for MgOx, it had a predominantly basic character that led to the production of the condensation product of one molecule of furfural and one molecule of acetone, and thus resulted in a lower selectivity to furfuryl alcohol. The TiOx solid was found to be mainly acidic and exhibited both Lewis and Brönsted acid sites. The presence of the latter could account for the lower selectivity to furfuryl alcohol. All in all, these results seemed to suggest that the MPV reaction is favored on Lewis acid sites and especially on acid–base pair sites. The process was accelerated under microwave irradiation.

Hydration of α-pinene catalyzed by acid clays

The hydration reaction of α-pinene in the presence of natural clays treated with monochloroacetic acid as catalyst to obtain oxygenated compounds was studied. Catalysts were characterized using X-ray diffraction, differential thermal analysis, programmed thermal desorption of adsorbed pyridine, and infrared spectroscopic analysis of adsorbed pyridine to determine Brønsted and Lewis acid sites. Catalytic tests revealed that treatment of the natural clay with the acid improved the catalytic activity and the selectivity toward oxygenated products by increasing the acidity of the catalyst. The selectivity toward oxygenated compounds increased with the augment of the α-pinene conversion because of greater contact between water molecules with the remaining α-pinene molecules. The natural clay without treatment produced compounds resulting from α-pinene isomerization, whereas the treated clays produced alcohols and other products in addition to isomerization compounds. After a certain time, the α-terpineol was isomerized into cineols. Studies of the reusability of the JAL catalyst were performed (clay treated with monochloroacetic acid). As the number of reuses increased, the percent conversion decreased; however, the selectivity toward oxygenated compounds increased.