Ingo Hartmann

The recycling of catalysts has emerged as a key solution to address environmental pollution and the scarcity of natural resources. This dynamic is further reinforced by the growing industrial demand for catalysts and the urgent need to transition to more sustainable production methods. In the context of chemical transformations, the direct reuse of recycled catalysts for chemical applications in particular represents an elegant route towards greener syntheses. In this article, we review recent advancements in the recycling of homogeneous and heterogeneous catalysts since 2020, emphasizing the utilization of waste-derived catalysts for chemical reactions. In particular, we consider three primary sources of waste: electronic waste, spent lithium-ion batteries, and industrial wastewater. For each of these waste streams, different extraction methods are explored for their effectiveness in obtaining catalysts suitable for a broad spectrum of chemical reactions. These presented studies emphasize the potential of recycled catalysts to contribute to a sustainable and waste-efficient future.

In view of the tremendous emissions of toxic gases and particulate matter (PM) by low-power firewood-fueled fireplaces, there is an urgent need for effective measures to lower emissions to keep this renewable and economical source for private home heating available in the future. For this purpose, an advanced combustion air control system was developed and tested on a commercial fireplace (HKD7, Bunner GmbH, Eggenfelden, Germany), complemented with a commercial oxidation catalyst (EmTechEngineering GmbH, Leipzig, Germany) placed in the post-combustion zone. Combustion air stream control of the wood-log charge combustion was realized by five different control algorithms to describe all situations of combustion properly. These control algorithms are based on the signals of commercial sensors representing catalyst temperature (thermocouple), residual oxygen concentration (LSU 4.9, Bosch GmbH, Gerlingen, Germany) and CO/HC-content in the exhaust (LH-sensor, Lamtec Mess- und Regeltechnik für Feuerungen GmbH & Co. KG, Walldorf (Germany)). The actual flows of the combustion air streams, as calculated for the primary and secondary combustion zone, are adjusted by motor-driven shutters and commercial air mass flow sensors (HFM7, Bosch GmbH, Gerlingen, Germany) in separate feedback control loops. For the first time, the residual CO/HC-content (CO, methane, formaldehyde, etc.) in the flue gas is in-situ monitored with a long-term stable AuPt/YSZ/Pt mixed potential high-temperature gas sensor, which allows continuous estimation of the flue gas quality with an accuracy of about ±10%. This parameter is not only an essential input for advanced combustion air stream control but also provides monitoring of the actual combustion quality and logging of this value over a whole heating period. By many firing experiments in the laboratory and by field tests over four months, it could be demonstrated that with this long-term stable and advanced automated firing system, depression of the gaseous emissions by about 90% related to manually operated fireplaces without catalyst could be achieved. In addition, preliminary investigations at a firing appliance complemented by an electrostatic precipitator yielded PM emission depression between 70% and 90%, depending on the firewood load.

The synthesis and characterization of sol-gel-derived cornhusk support for low-temperature catalytic methane combustion (LTCMC) were investigated in this study. The prepared cornhusk support was impregnated with palladium and cerium oxide (Pd/CeO₂) via the classical incipient wetness method. The resulting catalyst was characterized using various techniques, including X-ray diffraction (XRD), N₂ physisorption (BET), transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H₂-TPR). The catalytic performance of the Pd/CeO₂/CHSiO₂ catalyst was evaluated for methane combustion in the temperature range of 150–600 °C using a temperature-controlled catalytic flow reactor, and its performance was compared with a commercial catalyst. The results showed that the Pd/CeO₂ dispersed on SiO₂ from the cornhusk ash support (Pd/CeO₂/CHSiO₂) catalyst exhibited excellent catalytic activity for methane combustion, with a conversion of 50% at 394 °C compared with 593 °C for the commercial silica catalyst (Pd/CeO₂/commercial). Moreover, the Pd/CeO₂/CHSiO₂ catalyst displayed better catalytic stability after 10 h on stream, with a 7% marginal loss in catalytic activity compared with 11% recorded for the Pd/CeO₂/commercial catalyst. The N₂ physisorption and H₂-TPR results indicated that the cornhusk SiO₂ support possessed a higher surface area and strong reducibility than the synthesized commercial catalyst, contributing to the enhanced catalytic activity of the Pd/CeO₂/SiO₂ catalyst. Overall, the SiO₂ generated from cornhusk ash exhibited promising potential as a low-cost and environmentally friendly support for LTCMC catalysts.

The quality of wood combustion processes can be effectively improved by achieving the automated control of the combustion air feed. For this purpose, continuous flue gas analysis using in situ sensors is essential. Besides the successfully introduced monitoring of the combustion temperature and the residual oxygen concentration, in this study, in addition, a planar gas sensor is suggested that utilizes the thermoelectric principle to measure the exothermic heat generated by the oxidation of unburnt reducing exhaust gas components such as carbon monoxide (CO) and hydrocarbons (C_xH_y). The robust design made of high-temperature stable materials is tailored to the needs of flue gas analysis and offers numerous optimization options. Sensor signals are compared to flue gas analysis data from FTIR measurements during wood log batch firing. In general, impressive correlations between both data were found. Discrepancies occur during the cold start combustion phase. They can be attributed to changes in the ambient conditions around the sensor housing.

Utilization of biomass either as a renewable energy source or for the generation of biogenic materials has received considerable interest during the past years. In the case of rice husk (RH) and rice straw (RS) with high silica contents in the fuel ash, these approaches can be combined to produce high-grade biogenic silica with purities >98 wt % from combustion residues. The overall process can be considered nearly neutral in terms of CO₂ emission and global warming, but it can also address disposal challenges of rice husk and rice straw. For the resulting biogenic silica, several advanced application opportunities exist, e.g., as adsorbents, catalysts, drug delivery systems, etc. This article provides a comprehensive literature review on rice husk and rice straw combustion as well as applied strategies for raw material pre-treatment and/or post-treatment of resulting ashes to obtain high quality biogenic silica. Purity of up to 97.2 wt % SiO₂ can be reached by combustion of untreated material. With appropriate fuel pre-treatment and ash post-treatment, biogenic silica with purity up to 99.7 wt % can be achieved. Studies were performed almost exclusively at a laboratory scale.

The separation of Pd and CeO₂ on the inner surface of controlled porous glass (CPG, obtained from phase-separated borosilicate glass after extraction) yields long-term stable and highly active methane combustion catalysts. However, the limited availability of the CPG makes such catalysts highly expensive and limits their applicability. In this work, porous silica obtained from acid leached rice husks after calcination (RHS) was used as a sustainable, cheap and broadly available substitute for the above mentioned CPG. RHS-supported Pd-CeO₂ with separated CeO₂ clusters and Pd nanoparticles was fabricated via subsequent impregnation/calcination of molten cerium nitrate and different amounts of palladium nitrate solution. The Pd/CeO₂/RHS catalysts were employed for the catalytic methane combustion in the temperature range of 150–500 °C under methane lean conditions (1000 ppm) in a simulated off-gas consisting of 9.0 vol% O₂, and 5.5 vol% CO₂ balanced with N₂. Additionally, tests with 10.5 vol% H₂O as co-feed were carried out. The results revealed that the RHS-supported catalysts reached the performance of the cost intensive benchmark catalyst based on CPG. The incorporation of Pd-CeO₂ into RHS additionally improved water-resistance compared to solely Pd/CeO₂ lowering the required temperature for methane combustion in presence of 10.5 vol% H₂O to values significantly below 500 °C (T₉₀ = 425 °C).

Combustion of solid biomass fuels for heat generation is an important renewable energy resource. The major part among biomass combustion applications is being played by small-scale systems like wood log stoves and small wood pellet burners, which account for 75% of the overall biomass heat production. Despite an environmentally friendly use of renewable energies, incomplete combustion in small-scale systems can lead to the emission of environmental pollutants as well as substances which are hazardous to health. Besides particles of ash and soot, a wide variety of gaseous substances can also be emitted. Among those, polycyclic aromatic hydrocarbons (PAH) and several organic volatile and semi-volatile compounds (VOC) are present. Heterogeneous catalysis is applied for the reduction of various gaseous compounds as well as soot. Some research has been done to examine the application of catalytic converters in small-scale biomass combustion systems. In addition to catalyst selection with respect to complete oxidation of different organic compounds, parameters such as long-term stability and durability under flue gas conditions are considered for use in biomass combustion furnaces. Possible catalytic procedures have been identified for investigation by literature and market research. Experimental studies with two selected oxidation catalysts based on noble metals have been carried out on a wood log stove with a retrofit system. The measurements have been performed under defined conditions based on practical mode of operation. The measurements have shown that the catalytic flue gas treatment is a promising method to reduce carbon monoxide and volatile organic compounds. Even a reduction of particulate matter was observed, although no filtering effect could be detected. Therefore, the oxidation of soot or soot precursors can be assumed. The selected catalysts differed in their activity, depending on the compound to be oxidized. Examinations showed that the knitted wire catalyst showed better activity for the reduction of carbon monoxide, whereas the honeycomb induced a higher reduction of aromatic compounds. The properties of the two catalysts can be combined by integrating both together. The one drawback of the catalyst so far is the deactivation for the conversion of methane.

Kleinfeuerungsanlagen, die mit fester Biomasse betrieben werden, können in nicht unerheblichem Umfang toxische bzw. gesundheitsgefährdende Schadgase sowie Feinstaub emittieren. Eine repräsentative Auswahl der am Markt verfügbaren oder in aktuellen Forschungsprojekten in der Entwicklung befindlichen sekundären Emissionsminderungstechniken wird vorgestellt. Zurzeit ist kein System zur sekundären Emissionsminderung am Markt verfügbar, das den Ausstoß sowohl gasförmiger als auch fester bzw. kondensierter Luftschadstoffe wirksam vermindert. Eine Recherche zum Stand von Wissenschaft und Technik zeigt, dass elektrostatische Abscheider in Kombination mit der katalytischen Abgasreinigung eine aussichtsreiche sekundäre Technik darstellen. Experimentelle Arbeiten zur Untersuchung einer solchen Kombination werden vorgestellt.