The valorization of lignin that derives as by product in various biomass conversion processes has become a major research and technological objective. The potential of the production of valuable mono-aromatics (BTX and others) and (alkyl)phenols by catalytic fast pyrolysis of lignin is investigated in this work by the use of ZSM-5 zeolites with different acidic and porosity characteristics. More specifically, conventional microporous ZSM-5 (Si/Al = 11.5, 25, 40), nano-sized (≤20 nm, by direct synthesis) and mesoporous (9 nm, by mild alkaline treatment) ZSM-5 zeolites were tested in the fast pyrolysis of a softwood kraft lignin at 400-600°C on a Py/GC-MS system and a fixed-bed reactor unit. The composition of lignin (FT-IR, 2D HSQC NMR) was correlated with the composition of the thermal (non-catalytic) pyrolysis oil, while the effect of pyrolysis temperature and catalyst-to-lignin (C/L) ratio, as well as of the Si/Al ratio, acidity, micro/mesoporosity and nano-size of ZSM-5, on bio-oil composition was thoroughly investigated. It was shown that the conventional microporous ZSM-5 zeolites are more selective toward mono-aromatics while the nano-sized and mesoporous ZSM-5 exhibited also high selectivity for (alkyl)phenols. However, the nano-sized ZSM-5 zeolite exhibited the lowest yield of organic bio-oil and highest production of water, coke and non-condensable gases compared to the conventional microporous and mesoporous ZSM-5 zeolites.
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http://dx.doi.org/10.3389/fchem.2018.00295 | DOI Listing |
J Colloid Interface Sci
January 2025
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, PR China; Yunnan Provincial Key Laboratory of Energy Saving in Phosphorus Chemical Engineering and New Phosphorus Materials, Kunming 650500, PR China. Electronic address:
Phosphorus (P)-doping H-ZSM-5 zeolites, which is crucial for industrial applications, aim to adjust both acidity and framework stability while optimizing product distribution in heterogeneous catalysis. Nonetheless, current phosphating methods often suffer from inadequate phosphorus dispersion and unclear interfacial interactions with framework aluminum (Al). In this work, P-doping ZSM-5 zeolites were successfully one-step prepared by using tributylphosphine served as an organophosphorus precursor, assisting by density functional theory calculations.
View Article and Find Full Text PDFScience
January 2025
Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford, UK.
The distribution of substitutional aluminum (Al) atoms in zeolites affects molecular adsorbate geometry, catalytic activity, and shape and size selectivity. Accurately determining Al positions has been challenging. We used synchrotron resonant soft x-ray diffraction (RSXRD) at multiple energies near the Al K-edge combined with molecular adsorption techniques to precisely locate "single Al" and "Al pairs" in a commercial H-ZSM-5 zeolite.
View Article and Find Full Text PDFJ Phys Chem C Nanomater Interfaces
January 2025
Center for Materials Science and Nanotechnology (SMN), Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, Oslo N-0315, Norway.
The flexibility of the H-ZSM-5 zeolite upon adsorption of selected coke precursors was investigated using both theoretical and experimental approaches. Four structural models with varying active site locations were analyzed through density functional theory (DFT) simulations to determine their responses to different types and quantities of aromatic molecules. Complementary experimental analysis was performed, allowing for a direct comparison with the theoretical findings, using thermogravimetric analysis (TGA), nitrogen adsorption (N adsorption), solid-state NMR, and X-ray diffraction (XRD).
View Article and Find Full Text PDFInorg Chem
January 2025
State Key Laboratory of Molecular & Process Engineering, SINOPEC Research Institute of Petroleum Processing, Beijing 100083, China.
The ZSM-5 zeolite is the key active component in high-severity fluid catalytic cracking (FCC) catalysts and is routinely activated by phosphorus compounds in industrial production. To date, however, the detailed structure and function of the introduced phosphorus still remain ambiguous, which hampers the rational design of highly efficient catalysts. In this work, using advanced solid-state NMR techniques, we have quantitatively identified a total of seven types of P-containing complexes in P-modified ZSM-5 zeolite and clearly revealed their structure, location, and catalytic role.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
UK Catalysis Hub, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, OX11 0FA, UK.
Methanol adsorption isotherms of fresh f-ZSM-5 and steamed s-ZSM-5 (Si/Al ≈ 40) are investigated experimentally at room temperature under equilibrium and by grand canonical Monte Carlo (GCMC) simulations with the aim of understanding the adsorption capacity, geometry and sites as a function of steam treatment (at 573 K for 24 h). Methanol adsorption energies calculated by GCMC are complemented by density functional theory (DFT) employing both periodic and quantum mechanics/molecular mechanics (QM/MM) techniques. Physical and textural properties of f-ZSM-5 and s-ZSM-5 are characterised by diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) and N-physisorption, which form a basis to construct models for f-ZSM-5 and s-ZSM-5 to simulate methanol adsorption isotherms by GCMC.
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