The biorefinery concept of lignocellulosic biomass with focus on thermochemical conversions will be presented and discussed with respect to the advantages, impacts, and methods. Analytics regarding the reaction mechanisms for the decomposition of cellulose, hemicellulose and lignin, respectively, will be presented along with new trends and perspectives within plasma and catalytic pyrolysis of lignin-fractions, artificial neural networks, hydrothermal liquefaction, torrefaction, gasification and combustion, pyrolysis and hydro pyrolysis as well as supercritical fluids for the catalytic thermochemical conversion of biomass and co-processing of upgraded bio-oil in fluidized catalytic cracking (FCC). A few examples are mentioned at this point; however, more details are given in the respective chapters. Concerning the catalytic conversion of lignin fractions the concept of the "catalyst philosophy" has been adapted from crude oil refining by using the hierarchical pore structure of the catalyst to arrive at the desired final products, like fuelcomponents or phenols. As a consequence, the same hierarchical catalysts can be applied in the co-processing of bio-oil with crude oil refined fractions. As a preliminary conclusion, the thermochemical conversion of lignocellulosic biomass has already reached a certain level of insight and understanding, however, there is still room for improvement and even a better understanding, and, last but not least, an upscaling to an industrial scale remains.

The lifetime achievements of Prof. Dr.-Ing. Jens Weitkamp are honored covering his education and career, his outstanding scientific contributions related to the fields of catalysis and porous materials, his scientific recognitions and services in a number of academic offices as well as his strong engagement with respect to the promotion of science and engineering.

This contribution is based on the monograph entitled “Recent Advances in Thermochemical Conversion of Biomass”, covering both general items as well as the primary processes, like fast pyrolysis, gasification, hydrothermal liquefaction, carbonization and secondary processes, like co-processing of bio-oil in fluidized catalytic cracking (FCC), Fischer-Tropsch synthesis and valorization of lignin [1].

Efficient thermochemical conversion of ligno-cellulosic biomass towards compatible liquid fuels like diesel and gasoline, potentially alcohols and ethers, is a story about new opportunities and challenging chemistry. Innovations of enabling materials (catalysts, adsorbents, membranes), efficient processing schemes, robust products portfolios and smart business strategies are needed to close the priority gap between fossil and the more complex renewable resources. Co-production of (platform) chemicals and bio-products can improve the economical basis. Options for thermochemical processing towards fuels include the pyrolysis route, which is proceeding via bio-oil (BO) upgrading, and the alternative gasification route, which is proceeding via syngas followed by catalytic synthesis, e.g. Fischer-Tropsch. The number of conditioning and conversion steps that can be envisaged along both routes needs to be minimized. Basic pretreatment of raw BO is chemical stabilization, which enables its storage or transport. More advanced upgrading is required to reach oil qualities suitable for heat and power, and even more advanced for transport applications (including aviation fuel). Catalysts and hydrogen can provide the required processing flexibility and product quality. Catalytic hydrodeoxygenation (HDO) is one of the most attractive upgrading options, enabling removal of heteroatoms, adding energy, and chemical transformations for tuning of properties. This review focuses on HDO and the catalytic properties of metal carbides, nitrides and phosphides, the potential of mesoporous-based catalytic materials, and also of noble metals. An overview of matured hydrotreating (HT) technology and conventional catalysts for HDS is provided as the benchmarking technology for developments towards increased biomass utilization.

In this work, different metal oxides (MO) supported on two types of zeolites: 1) natural clinoptilolite (NZ) and 2) synthetic zeolite, ZSM-5 were prepared and tested as catalysts in the fast pyrolysis of hardwood lignin. NZ was modified with the CaO and MgO by a simple two steps procedure consisting of an ion exchange reaction and a subsequent calcination at 773 K. The synthetic ZSM-5 was modified with several MO species (Ni, Cu, Ca, Mg) by a wet impregnation and calcination at 873 K. ?he prepared catalysts were characterized by X-ray diffraction analysis (XRD), scanning electron microscopy and energy dispersive X-ray analysis (SEM/EDS) and measurement of specific surface area (BET method). Acid sites were characterized and quantified by pyridine (py) absorption using Fourier transform infrared spectroscopy (FTIR). The catalysts exhibit catalytic activity depanding on modification, reaction temperature and of the MO contents. The highest yield of useful phenol in bio-oil was obtained with NiO/ZSM-5 (34.8 wt.%) which exhibits the highest specific surface area and the highest concetration of Br?nsted and Lewis acid sites. The studied catalysts did not increase significantly the content of polycyclic aromatic hydrocarbons (PAHs) and heavy compounds compared to non-catalytic experiment.

Co-pyrolysis of bisphenol A polycarbonate with lignoboost (regular and modified) lignin from softwood and with organosolv lignin from hardwood was performed in a semi-batch reactor at 500 degrees C and self-generated pressure. Catalytic upgrading was performed at 300 degrees C over MCM-41 and SBA-15 catalysts. The effect consisted in conversion of bisphenol A into phenol and its light derivatives. Hydrogenation occurred during upgrading based on the hydrocarbons converted into coke on the surface of catalysts. The Al-MCM41 with Si/Al ratio of 16 (MCM16) and Al-SBA-15 with Si/Al ratio of 48 (SBA 48) catalysts had similar effects for the lignoboost lignins, with slight advantage for the MCM16 in the case of regular lignoboost while MCM16 was clearly the best one for the organosolv lignin in converting the heavier compounds into lighter ones. (c) 2014 Elsevier Ltd. All rights reserved.

•Synthesis of TiO2 supported carbide, nitride and phosphide catalysts.•Catalysts were active for phenol HDO with promising selectivity.•The 15wt% Mo2C/TiO2 showed the highest activity (crystals 10–30nm).•Moderate deactivation was observed (15wt% Mo2C/TiO2 during 400min.).•Supported MoP showed the highest hydrogenation activity.

In this study the catalytic activity of Na-rich and MO-containing natural clinoptilolite (MO - nanopartides of NiO, ZnO, or Cu2O) was studied in the pyrolysis of hardwood lignin. The clinoptilolite samples exhibit different catalytic activities which depend mainly on the type of the nano-oxide. The presence of nano-oxides did not affect the porosity of the clinoptilolite framework but influenced its acidity. However, it seems that acidity of the lattice did not influence the catalytic activity of the clinoptilolite in the pyrolisis of hardwood lignin. The number of Lewis acid sites increased significantly for the ZnO- and Cu2O-containing clinoptilolite whereas for the NiO-sample it did not change appreciably in comparison to the parent zeolite. The amount of phenols in the as-produced bio-oil varies from 39% for ZnO-clinoptilolite, 43% for Na-rich clinoptilolite, to 50 and 54% for Cu2O- and NiO-containing samples, respectively. The highest yield of phenols obtained in the presence of NiO-containing clinoptilolite is ascribed to a synergetic interaction of the clinoptilolite lattice and nano-NiO particles. (C) 2013 Elsevier Inc. All rights reserved.

The chapter addresses the thermochemical conversion route of lignocellulosic material to bio-oil, and presents an overview of research on its further catalytic upgrading toward compatible transport fuels and products within the biorefinery. The state of this still noncommercial technology is sought and defined, and particular challenges along the route are highlighted. The information provided includes bio-oil production by fast pyrolysis and liquefaction, and typical characteristics and particularly challenging features of bio-oils compared to conventional oil. Conventional hydrotreating approaches for desulfurization are briefly mentioned as an introduction to the challenges to catalytic (hydro)deoxygenation (HDO chemistry). The chapter concludes with a discussion on the future prospects for commercial implementation and an evaluation of the hurdles that remain, which includes the still too high capital costs and complex feedstocks imposing technological complexity, as well as the requirement for establishing benefits of scale.

An experimental investigation on a vapor phase adsorptive desulfurization process for diesel is described based on NiMCM-41 and NiY as sulphur selective adsorbents. Under optimized conditions [ pressure 4 bar (absolute) and temperature 350 degrees C] the NiMCM-41 adsorbent could bring down the sulphur concentration to a 50 ppm level from a concentration of 450 ppm in a refinery diesel, and about 20 ml of diesel could be treated per gram of adsorbent. With a diesel feed of 150 ppm sulphur, the same adsorbent could bring the sulphur down to 15 ppm level and about 14 ml of the feed could be treated per gram of the adsorbent. The performance of NiY is slightly better than NiMCM-41. Around 25 ml diesel feed could be treated per gram NiY adsorbent in bringing down the sulphur levels from 450 ppm to <50 ppm. Both these adsorbents are regenerable under controlled oxidation with air at similar to 450 degrees C without noticeable loss in the sulphur removal capacity. The regeneration conditions were established based on a temperature programmed oxidation (TPO) study on spent diesel adsorbents. (C) 2012 Elsevier Ltd. All rights reserved.

The main energy supply is shifting from oil-based to more natural gas-based since the depletion of crude oil reserves. The non-oxidative direct methane aromatisation over zeolite supported molybdenum bifunctional catalysts produces benzene, toluene, and xylenes as desired products, and hydrogen as a valuable by-product [1]. It was suggested that the original Mo ions in the zeolite are reduced and carbided to Mo2C during the initial induction period [2]. The methane activation occurs on the Mo2C sites forming ethene then, the oligomerisation of ethene takes place on acid sites producing benzene. The aim of the present work was to perform an in-depth investigation of the methane aromatisation kinetics and develop fundamental model to describe the dynamic reaction kinetics.