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Eingeladener Vortrag
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A major industrial reaction based on homogeneous catalysis is hydroformylation for the production of aldehydes from alkenes and syngas. Hydroformylation in microemulsions, which is currently under investigation at Technische Universität Berlin on a mini-plant scale, was identified as a cost efficient approach which also enhances product selectivity. Herein, we present the application of online Raman spectroscopy on the reaction of 1-dodecene to 1-tridecanal within a microemulsion. To achieve a good representation of the operation range in the mini-plant with regard to concentrations of the reactants a design of experiments was used. Based on initial Raman spectra partial least squares regression (PLSR) models were calibrated for the prediction of 1-dodecene and 1-tridecanal. Limits of predictions arise from nonlinear correlations between Raman intensity and mass fractions of compounds in the microemulsion system. Furthermore, the prediction power of PLSR models becomes limited due to unexpected by-product formation. Application of the lab-scale derived calibration spectra and PLSR models on online spectra from a mini-plant operation yielded promising estimations of 1-tridecanal and acceptable predictions of 1-dodecene mass fractions suggesting Raman spectroscopy as a suitable technique for process analytics in microemulsions.
UV-induced transformation of dissolved
organic matter (DOC) is often accompanied by reduction
of molecular weight and aromaticity and an increase of
low-molecular weight (LMW) matter that can be utilized as
a substrate by heterotrophic bacteria. Moreover, the generation
of reactive transients and mineralization of DOC
occurs. For a better understanding of the modification that
starts after irradiation and to distinguish between possible
chemical and biological modifications, we selected different
natural organic matter (NOM) from Norway and
Germany. The aqueous solutions were treated by UV
irradiation and divided into two aliquot samples. NaN3
anti-bacterial treatment was applied to one sample, and
high-pressure size-exclusion chromatography (HPSEC)
analysis was used for both. In all samples, we found typical
modifications of NOM after UV irradiation. Incubation
(>7 days) of UV-irradiated NOM samples resulted in
lower levels of LMW matter and increased aromaticity.
Parallel to these changes of carbon fractions, an increase in
bacterial cell numbers was observed. Addition of NaN3 to
NOM, however, inhibited the reduction of LMW matter,
indicating that microbial activity accounted for the
observed changes in NOM. Analysis of the bacterial
community composition by denaturing gradient gel electrophoresis
(DGGE) of the amplified 16S rRNA genes
revealed that bacterial communities of non-irradiated and
UV-irradiated NOM were different and that UV selected
for specific members of α-proteobacteria, β-proteobacteria,
and Bacteriodetes. Our results imply that after UV-irradiation
of NOM, specific bacterial members are well adapted
to low pH, high LMW DOC concentrations, and oxidative
stress, and therefore thrive well on UV-irradiated humic
matter.