Combination of non-thermal plasma and heterogeneous catalysis for oxidation of volatile organic compounds: Part 2. Ozone decomposition and deactivation of γ-Al2O3

The role of ozone was studied for two different configurations combining non-thermal plasma (NTP) and heterogeneous catalysis, namely the use of a gas phase plasma with subsequent exposure of the effluent to a catalyst in a packed-bed reactor (post-plasma treatment) and the placement of the catalyst directly in the discharge zone (in-plasma catalysis). Non-porous and porous alumina and silica were deployed as model catalysts. The oxidation of immobilised hydrocarbons, toluene as a volatile organic compound and CO as an inorganic pollutant were studied in both operational modes.

While conversion and selectivity of hydrocarbon oxidation in the case of catalytic post-plasma treatment can be fully explained by the catalytic decomposition of O₃ on γ-Al₂O₃, the conversion processes for in-plasma catalysis are more complex and significant oxidation was also measured for the other three materials (-Al₂O₃, quartz and silica gel). It became obvious that additional synergetic effects can be utilised in the case of in-plasma catalysis due to short-lived species formed in the NTP.

The capability of porous alumina for ozone decomposition was found to be correlated with its activity for oxidation of carbon-containing agents. It could be clearly shown that the reaction product CO₂ poisons the catalytic sites at the γ-Al₂O₃ surface. The catalytic activity for O₃ decomposition can be partially re-established by NTP treatment. However, for practical purposes the additional reaction pathways provided by in-plasma catalytic processes are essential for satisfactory conversion and selectivity.     

Adsorbent Regeneration by Non‐thermal Plasma for Elimination of Odorous Compounds from Indoor Air

The non‐thermal plasma (NTP) technique was shown to be a method to improve indoor air quality. In particular in kitchens, odorous emissions can be removed by NTP. A combined concept of adsorption of volatile organic compounds (VOCs) and plasma regeneration of the adsorber was tested in adsorption‐regeneration‐adsorption cycles. As reference VOCs, 2‐methylthiophene, 2‐methylpyrazine, 2‐acetylthiazole, nonanal, and trans‐2‐nonenal were selected in humid air streams. These odorous compounds are emitted during cooking and frying processes. The adsorption‐regeneration concept was also tested during a simulated frying process with garlic in rape oil. A hydrophobic zeolite was chosen as adsorber material and placed directly into the discharge zone of a plasma reactor.     

Chemikalienfreie Bekämpfung von Holzschädlingen durch dielektrische Erwärmung mit Radiowellen und Mikrowellen

Thermal pest control requires long treatment times due to the low thermal conductivity of wood and may lead to the formation of cracks. Here, the thermal treatment with radio waves as well as microwaves has been studied. The direct dielectric heating has the advantage of a good homogeneity. The obtained temperature profiles for radio waves were more homogeneous compared to microwaves. Detailed studies showed that elimination of pests was not related to the application of the electromagnetic field itself, but due to the temperature increase.     

Sorption of pyrene to dissolved humic substances and related model polymers. 2. Solid-phase microextraction (SPME) and fluorescence quenching technique (FHT) as analytical methods

Sorption coefficients for pyrene on dissolved humic substances and on poly(acrylic acid) esters as well-defined model polymers were determined using solid-phase microextraction (SPME) and the fluorescence quenching technique (FQT). The results of both analytical methods were compared and theoretically evaluated, which led to the conclusion that the sorption coefficients measured by SPME and FQT are inevitably different: SPME measures activity-based and FQT concentration-based sorption coefficients. The environmental relevance of the two types of sorption coefficients is discussed. FQT is inappropriate to measure sorption coefficients for pyrene with the synthetic sorbents. Inspection of the vibrational structure of the fluorescence spectra of those solutions indicates a highly hydrophobic microenvironment of pyrene. This can be explained by an intra- or intermolecular agglomeration of hydrophobic moieties forming a favorable host for hydrophobic solutes.     

Combining Different Frequencies for Electrical Heating of Saturated and Unsaturated Soil Zones

In situ electrical heating of soil was studied applying different frequencies: low‐frequency energy for resistive heating and radio‐frequency energy for dielectric heating. Steep temperature gradients were observed for each heating mode under the condition of the coexistence of saturated and unsaturated soil zones. By combining the two heating modes, this undesired effect can be avoided, thus allowing efficient soil remediation especially when organic phases are accumulated at the capillary fringe. A parallel application of both frequencies was demonstrated as the most suitable method to reduce temperature gradients. By using electronic filters, both electric fields can be established by only one electrode array. This innovative concept is especially applicable for optimizing thermal remediation of light non‐aqueous phase liquid contaminations or realizing thermally‐enhanced electrokinetic removal of heavy metals.     

Konzepte zur Grundwasserreinigung

Concepts for Groundwater Purification Contamination of water‐bearing strata is, in contrast to the contamination of surface waters, for most people not noticeable. However this does not lead, at least in Germany, to reduced awareness about the problem, as drinking water and groundwater are closely connected in the public’s mind. The cleanup of contaminated groundwater is generally aimed at a negligibly low or tolerable remaining risk for the subjects of the protection. The goals of the cleanup should always be considered in the light of the appropriateness of the time and effort involved and the environmental balance of cleanup measures. Otherwise there is the danger that technical environmental protection however well meant is directed against the environment, because the associated use of resources is greater than that for the protection or regeneration at which it is targeted. Different cleanup concepts are represented in the order of decreasing intensity of the technical measures.     

Engineering aspects of radio-wave heating for soil remediation and compatibility with biodegradation

Dielectric heating of soil using radio waves (RW) can be applied to support various remediation techniques, namely biodegradation and soil vapor extraction, under in situ, on site or ex situ conditions. To improve the spatial resolution of energy dissipation, the design of rod electrodes was modified with an air gap around the electrode allowing thermal treatment focused to the desired soil volume. A combination of low- and high-frequency electrical energy was successfully applied to homogeneously heat the capillary fringe, the boundary region of saturated and unsaturated zones. The energetic efficiency of the method was evaluated showing that an efficient transformation of RW energy to heat in the target volume can be achieved. By comparing biodegradation and soil respiration under conventional and electric (low-frequency resistive and dielectric RW) heating, the compatibility of the electric heating methods with bioremediation processes could be proven. Therefore, RW-supported microbial degradation of pollutants is a real option for accelerated soil remediation.     

Untersuchungen zur Sulfochlorierung von Paraffinen. IV. Über die Sulfochlorierung von Isobutan

Studies on Sulphochlorination of Paraffins. IV. On the Sulphochlorination of Isobutane In the sulphochlorination of isobutane at −20 to −10°C a mixture of 20–25% tert.-butyl and 75–80% of isobutyl sulphochlorides is formed. The mixture has been analyzed by ¹H- and by ¹³C-n.m.r.-spectroscopy. It is possible to transform the mixture of sulphochlorides into mixtures of the corresponding sulphonates, sulphonic acid methyl esters or sulphonic acid demithylamides. During the work-up of the sulphochlorination mixtures it is necessary to keep the temperature low, because tertiary butyl sulphochloride is desulphonated at a noticeable rate already at temperatures above 35°C.     

Catalytic effects of activated carbon on hydrolysis reactions of chlorinated organic compounds: Part 2. 1,1,2,2-Tetrachloroethane

The hydrolysis reaction of 1,1,2,2-tetrachloroethane (TeCA) is significantly enhanced by sorption on activated carbon. TeCA is quantitatively transformed into trichloroethene (TCE) at moderate pH values. This transformation is exploited as the basic step of a site-adapted groundwater-cleanup technology. The volatility of TCE is a factor of 23 higher than that of TeCA such that the partially dehydrochlorinated product can be easily stripped out of the groundwater flow. The base-mediated and the neutral dehydrochlorination of TeCA were studied as a function of temperature and pH value in batch and column experiments. Surprisingly, it was found that despite high loadings of the sorbent with TeCA and TCE (≥20 wt.%) the TeCA remains available for the hydrolysis reaction.