Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters.

A series of 20 wt.% MO2/S catalysts (where M = Ce, Mn or Zr and S = SiO2 or Al2O3) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different methods (XRD, TPR and SBET). For the first time, anhydrides were used as potential starting materials for ketone synthesis. This novel reaction was performed on various aliphatic anhydrides in the presence of catalysts within a temperature range of 523-723 K. For all anhydrides, except for pivalic anhydride, the appropriate ketones were obtained with good or very good yields. The vapor-phase catalytic ketonization of esters of benzene-1,x-dicarboxylic acids (x = 2, 3 or 4) with acetic acid were studied in the range of 673-723 K in order to obtain 1,x-diacetylbenzenes. Their yields strongly increased with an increase in the x value (0, 8 and 43% for x = 2, 3 and 4, respectively). The presence of acetophenone as a side product was always noted. In the case of ω-phenylalkanoic acids, their vapor-phase ketonization with acetic acid led to the formation of appropriate ketones with 47-49% yields. Much lower yields of ketones (3-19%) were obtained for acids and ethyl esters containing heterocycle substituents (with O or S atoms) and/or vinyl groups. In the reaction between ethyl 4-nitrophenylacetate and acetic acid, only the products of ester decomposition (p-toluidine and p-nitrotoluene) were determined.

Possible Options for Utilization of EU Biomass Waste: Pyrolysis Char, Calorific Value and Ash Content.

The application of biomass as a co-feed in coal power plants and in standalone biomass power plants, as well as in char production for soil remediation, is a currently important issue. This paper reports on the investigation of biochar formation from agricultural waste crops that are used for soil upgrading, but which do not meet the standards of EU crops, as well as largescale food processing waste. These were compared to test results from basket willow, which is commonly used for energy generation. Food industry waste is often produced in cities on a large scale and is generally easier to process due to lack of other stream components. The key parameters, namely, the content of volatiles, energy content of the formed biochar and the composition of the ash, were determined for a number of herbaceous materials locally available in the European Union. All of them can be used as a cheap source of biochar. A novel procedure of capturing volatiles and hence minimizing the PAH content in the biochar, as well as enabling the recovery of energy from the volatiles is presented. Knowledge of the composition and form of elements in ash is very important for designing ash management systems if co-combustion is implemented. The aim of this study was to determine if the types of biomass are better suited for biochar production or energy generation.