In this study a H‐ZSM‐5 zeolite (Si/Al=11) was modified by a stepwise treatment with steam, sodium hydroxide and hydrochloric acid. During progressing dealumination by various treatment methods, the drawbacks of initial post‐synthetic steps, e. g. pore‐filling by steam dealumination, are compensated by subsequent steps, e. g. washing by acid, which leads to a scientifically based preparation of required ZSM‐5 zeolite. Solid‐state properties of as‐synthesized and modified zeolites are determined by structural (XRD, ICP‐OES, NMR), textural (physisorption, laser scattering) and acid sites analysis (TPAD). Consequently, extended dealumination without structural damage is demonstrated. Its origin by framework dealumination and pore cleaning is verified in ethanol to hydrocarbon process (ETH) by shape‐selective formation of coke and aromatics, characterized by “aromatics index” (AI).

In this study a commercial H-ZSM-5 zeolite (Si/Al = 11) was post-synthetically modified by a combined dealumination procedure to adjust its catalytic properties for the selective formation of aromatics from ethanol. The solid-state properties of original and modified zeolites are determined by structural, textural and acidity analysis. The formation of aromatics and durability of the zeolites were investigated depending on space velocity or contact time in the catalyst bed. In particular, the formation rate and desorption of aromatics from solid-state surface as well as their tendency to form coke precursors by consecutive build-up reactions determine the formation of coke. Therefore, the rate of buildup and finished aromatization by hydride transfer (predetermined by the kind, location and geometric arrangement of surface acid sites) and the statistical number of reaction events until final desorption at the specific contact time have to be harmonized to increase aromatics yield and to decrease catalyst decay by coke simultaneously.

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Aluminum‐based composite particles are widely applied complex catalyst materials in oil refining. Due to their tunable shape, porosity, and acidity, they are commonly used for the production of cracking catalysts. Shaping of well‐defined particles remains a challenge for industrial catalyst preparation by spray drying, because catalyst properties must satisfy local demands of a refinery. The selectivity can be modified and the cracking activity enhanced with acid binders, e.g., AlCl3. Therefore, peptization of AlCl3‐containing suspensions with zeolite Y and kaolin was characterized by pH value, 27Al NMR spectroscopy, and zeta potential. A new control strategy for binding of kaolin and zeolite Y in spray drying was developed by adjusting the pH and binder Al/Cl ratio.

Silica‐based composite particles are complex catalyst materials that are widely used in petrochemistry. The preparation of particles that are well defined in form, composition, and chemical and rheological behavior by spray drying of suspensions remains an important industrial challenge. Here, zeolite HY, kaolin, and the cheap binder water glass are used. Experimental and model regimes of slurry peptization are analyzed based on their pH value, zeta potential, and mixing speed to control the process. The results show a pseudoplastic behavior of the silica slurries for zeta potential below 20 mV, which is explained by surface charge, hydroxyls, and pH‐dependent coagulation. Thus, a quick acidification of the slurry, additional mechanic shear, and subsequent pH control during spray drying enable control of peptization kinetics.

The conversion of different biogenic feedstocks to hydrocarbons is a major challenge when ensuring hydrocarbon and fuel supply in spite of the heterogeneity of this feed. Flexible adaptation to changing compositions is mandatory for the respective processes. In this study, different oxygenate model feeds, such as alcohols, aldehydes, carboxylic acids and esters, were converted at 500 °C and 5 barg H2 using H-ZSM-5 zeolite catalysts with various Si/Al ratios to identify the relationship between the feed structure and the final product distribution. As the main outcome, the product distribution becomes increasingly independent of the feed structure for Al-rich H-ZSM-5 catalyst samples at low Time on Stream (ToS). Some minor exceptions are the increased formation of aromatics during ToS for carbonyl oxygenates compared to primary alcohols and the dominance of initial deoxygenation products for Si-rich H-ZSM-5 samples. This is interpreted by a multi-stage reaction sequence, which involves the initial deoxygenation of the feed and the subsequent integration of the olefin intermediates into a reaction network. The results pave the way towards the achievement of a desired product distribution in the conversion of different oxygenates simply by the adaption of the Al content of H-ZSM-5.

Conversion of ethanol to hydrocarbons by porous zeolite ZSM‐5 is a sustainable alternative compared to crude oil, gas or coal conversion. A quantification and description of micro‐ and macroscopic deactivation kinetics with basic transport and reactor models reveals deeper insight into the dynamics of coking and product formation at varying contact time. A new first order deactivation model helps to separate linear deactivation and autocatalytic acceleration of catalyst decay. A deeper look into product formation reveals a change in selectivity during initiation and deactivation phase from bigger build‐up C5+ to smaller cracking products C3 after formation of coke precursors, which does not coincide with site‐loss and reduction of contact time alone. Thereby, deactivation and switching selectivity in the hydrocarbon pool concept become more deterministic, which paves the way to more selective ethanol conversion processes.

The replacement of fossil carbon sources with green bio-oils promotes the importance of several hundred oxygenated hydrocarbons, which substantially increases the analytical effort in catalysis research. A multilinear regression is performed to correlate retention indices (RIs) and response factors (RFs) with structural properties. The model includes a variety of possible products formed during the hydrodeoxygenation of bio-oils with good accuracy (RRF2 0.921 and RRI2 0.975). The GC parameters are related to the detailed hydrocarbon analysis (DHA) method, which is commonly used for non-oxygenated hydrocarbons. The RIs are determined from a paraffin standard (C5–C15), and the RFs are calculated with ethanol and 1,3,5-trimethylbenzene as internal standards. The method presented here can, therefore, be used together with the DHA method and be expanded further. In addition to the multilinear regression, an increment system has been developed for aromatic oxygenates, which further improves the prediction accuracy of the response factors with respect to the molecular constitution (R2 0.958). Both predictive models are designed exclusively on structural factors to ensure effortless application. All experimental RIs and RFs are determined under identical conditions. Moreover, a folded Plackett–Burman screening design demonstrates the general applicability of the datasets independent of method- or device-specific parameters.