In-Situ Analysis of Volatile Organic Compounds in Biogas Fermentation Processes Using a Metal Oxide Gas Sensor Array (2020)

1. Introduction and Motivation Considering the global climate change, the efficient use of clean and renewable sources of energy is one of the key research areas. In this context, the biological production of methane and other combustible biogas produced by anaerobic fermentation of organic wastes is gaining growing importance. These fermentation processes attract more and more interest mainly due to the possibility to use different types of residues like food waste, dairy wastes and many other organic wastes as feeding substrates. However, efficient biomass conversion to biogas is only possible if the process parameters taking direct influence on the fermentation process are continuously and reliably monitored. This allows efficient process control. One of such key process parameters are the volatile fatty acids (acetic, propionic, butanoic) formed during the biomass conversion process. The reliable monitoring of such organic acids and other volatile organic compounds (VOCs) gives valuable information and their analysis even at low concentrations (&lt;2000 ppm) allows to model the actual microbial state and to adapt the feeding to keep their concentration and their inhibiting influence on the fermentation process low. Conventionally, the analysis of the organic acid composition in anaerobic fermentation processes is done by sophisticated methods like gas chromatography [1], infrared spectroscopy [2], and high pressure liquid chromatography (HPLC) [3]. However, the major disadvantages of these methods are their complicated and time consuming sample pre-treatment routines and high costs. In this paper, an automated measuring system developed by combining a silicon rubber membrane based carrier gas probe (Fig. 1) with a thermo-cyclically operated metal oxide gas sensor array [4] is introduced. This automated system might enable in-situ monitoring of different VOCs developing during the bio-fermentation processes in time periods of about one hour. 1. Method of VOC monitoring Metal oxide gas sensors (MOGs) are well established as gas sensing devices for monitoring of VOCs and oxidizable gases like CO, H 2 and CH 4 . Thus, before measurement of dissolved VOCs, CH 4 and other to cross-sensitivity contributing gas components present in the biogas fermentation sample must be driven out. In a first step, a small amount of the fermentation liquid (about one liter) is extracted from the main reactor and its pH is shifted to an alkaline value by dosage of potassium hydroxide. This allows transformation of the dissolved organic acids to the dissociated state and enables purging out CH 4 , H 2 and all other non-acidic, physically dissolved gas components contributing to the sensor signal, by a high flow of N 2 . Then, pH is shifted to a value near or even lower than the pKa value of the organic acids by dosage of phosphorous acid. Now the dissolved organic acids are in the undissociated molecular state and equilibrate with the gas state (Henry´s law). This enables the uptake of molecular dissolved organic acids from the liquid state into the constant flow of synthetic air (carrier gas: 5ml/min) by permeation through the gas permeable silicon rubber membrane of the gas carrier probe. By the help of the carrier gas the organic acids are transported to the metal oxide gas sensor array (Fig 1a) for analysis. 1. Results and Discussion Several SnO 2 /additive gas sensing composites have been prepared and the most interesting candidates with respect to their remarkably high sensitivity and most characteristic conductance vs. time profile (CTP) shapes when operated in thermocyclic mode [4,5] will be reported. When the carrier gas probe is immersed in acetic acid/deionized water admixtures some metal oxides show characteristic CTP-shapes (Fig. 1b) representing the individual surface reaction processes with acetic acid. In addition, some first experiments with real fermentation liquids resulted in some unexpected gas developments with pH and time well indicated by characteristic CTP-changes, which will highlight the presentation. 1. Conclusions and outlook By some extended in-situ monitoring experiments of acetic acid in deionized water as a model substance using a gas carrier probe combined with a 4-fold metal oxide sensor array, several metal oxide materials could be identified as good candidates for monitoring of organic acids in biogas fermentation processes. Monitoring experiments in real fermentation samples and analysis of the CTPs yielded gas formation changing with pH and time. These gas formation processes have to be referenced by simultaneous Gas Chromatograph-Mass Spectrometry (GC-MS) analysis and the results will be reported as well in context with the MOG sensitivity data. 1. Acknowledgement This work is part of the EBIPREP collaboration project (www.ebiprep.eu/). It is financed by the EU International Programme INTERREG V Oberrhein 2017-2020. References [1] V. Diamantis, P. Melidis, A. Aivasidis; Continuous determination of volatile products in anaerobic fermenters by on-line capillary gas chromatography, Analytica Chimica Acta 573-574(2006)189-194 [2] H.M. Falk, P. Reichling, C. Andersen, R. Benz; Online monitoring of concentration and dynamics of volatile fatty acids in anaerobic digestion processes with mid-infrared spectroscopy, Bioprocess Biosyst Eng (2015) 38:237-249 [3] P.v. Zumbusch, T. Meyer-Jens, G. Brunner, H. Märkl; On-line monitoring of organic substances with high-pressure liquid chromatography (HPLC) during the anaerobic fermentation of waste-water, Appl Microbiol Biotechnol (1994)42:140-146 [4] K. Frank, V. Magapu, V. Schindler (†), H. Kohler, H.B. Keller, R. Seifert; Chemical analysis with tin oxide gas sensors: choice of additives, method of operation and analysis of numeric signal, 7th East Asian Conference on Chemical Sensors, Dec. 3-5, 2007, Singapore, SENSOR LETTERS 6 (2008) 908-911. [5] Navas Illyaskutty, Jens Knoblauch, Matthias Schwotzer, Heinz Kohler; Thermally modulated multi sensor arrays of SnO2/additive/electrode combinations for enhanced gas identification, Sensors and Actuators B 217 (2015) 2-12 Figure 1