Synthesis of Zeolites from Fine-Grained Perlite and Their Application as Sorbents

The hydrothermal alteration of perlite into zeolites was studied using a two-step approach. Firstly, perlite powder was transformed into Na-P1 (GIS) or hydro(xy)sodalite (SOD) zeolites at 100 °C and 24 h using 2 or 5 M NaOH solutions. Secondly, the Si:Al molar ratio of the reacted Si-rich solution was adjusted to 1 by Na-aluminate addition to produce zeolite A (LTA) at 65 or 95 °C and 6 or 24 h at an efficiency of 90 ± 9% for Al and 93 ± 6% for Si conversion. The performance of these zeolites for metal ion removal and water softening applications was assessed by sorption experiments using an artificial waste solution containing 4 mmol/L of metal ions (Me(2+): Ca(2+), Mg(2+), Ba(2+) and Zn(2+)) and local tap water (2.1 mmol/L Ca(2+) and 0.6 mmol/L Mg(2+)) at 25 °C. The removal capacity of the LTA-zeolite ranged from 2.69 to 2.86 mmol/g for Me(2+) (=240–275 mg/g), which is similar to commercial zeolite A (2.73 mmol/g) and GIS-zeolite (2.69 mmol/g), and significantly higher compared to the perlite powder (0.56 mmol/g) and SOD-zeolite (0.88 mmol/g). The best-performing LTA-zeolite removed 99.8% Ca(2+) and 93.4% Mg(2+) from tap water. Our results demonstrate the applicability of the LTA-zeolites from perlite for water treatment and softening applications

Causes of abundant calcite scaling in geothermal wells in the Bavarian Molasse Basin, Southern Germany

The carbonate-dominated Malm aquifer in the Bavarian Molasse Basin in Southern Germany is being widely exploited and explored for geothermal energy. Despite favorable reservoir conditions, the use of geothermal wells for heat and power production is highly challenging. The main difficulty, especially in boreholes >3000 m deep with temperatures >120 °C, is that substantial amounts of calcite scales are hindering the proper operation of the pumps within the wells and of the heat exchangers at the surface. To elucidate the causes of scaling we present an extensive geochemical dataset from the geothermal plant in Kirchstockach. Based on chemical analyses of wellhead water samples, chemical and mineralogical analyses of scales collected along the uppermost 800 m of the production well, and chemical analyses of gas inclusions trapped in calcite-scale crystals, four processes are evaluated that could promote calcite scaling. These are (i) decompression of the produced fluid between the reservoir and the wellhead, (ii) corrosion of the casing that drives pH increase and subsequent calcite solubility decrease, (iii) gas influx from the geothermal reservoir and subsequent stripping of CO2 from the aqueous fluid, and (iv) boiling within the geothermal well. The effectiveness of the four scenarios was assessed by performing geochemical speciation calculations using the codes TOUGHREACT and CHILLER, which explicitly simulate boiling of aqueous fluids (CHILLER) and take into account the pressure dependence of calcite solubility (TOUGHREACT). The results show that process i causes notable calcite supersaturation but cannot act as the sole driver for scaling, whereas ii and iii are negligible in the present case. In contrast, process iv is consistent with all the available observations. That is, scaling is controlled by the exsolution of CO2 upon boiling at the markedly sub-hydrostatic pressure of 4–6 bar within the production well. This process is confirmed by the visible presence of gas inclusions in the calcite scales above the downhole pump, where the production fluid should nominally have been in the homogeneous liquid state. Whereas minor calcite scaling may have been triggered by fluid decompression within the production well, we conclude that the abundant scaling along the pump casing is due to cavitation induced by operating the pump at high production rates

Nachweis der thermischen Abbaubarkeit des Kalkinhibitors NC47.1B als Voraussetzung für den Einsatz im bayerischen Molassebecken

In der Metropolregion München soll bis 2040 der gesamte Wärmebedarf klimaneutral gedeckt werden. Ein Großteil dieser Wärme soll aus der tiefen Geothermie kommen. Schon heute werden hier zahlreiche Geothermieanlagen erfolgreich betrieben. Bei Thermalwasserförderraten von >100 l/s und Fördertemperaturen über 100 °C kommt es im bayerischen Molassebecken allerdings vermehrt zur Bildung von mineralischen Ausfällungen, welche den Betrieb und schließlich die Wirtschaftlichkeit beeinträchtigen. Die Ausfällungen bestehen größtenteils aus Carbonaten, weswegen der umweltfreundliche Kalkinhibitor NC47.1B zur Vorbeugung eingesetzt wird. Wirksamkeit und Effizienz des Kalkinhibitors wurden im Forschungsprojekt EvA-M nachgewiesen. Als Voraussetzung für einen dauerhaften Einsatz wird im Nachfolgeprojekt EvA-M 2.0 nun die Umweltverträglichkeit nachgewiesen. Diese setzt sich aus der nicht-toxischen Inhibitorchemie sowie der biologischen und thermischen Abbaubarkeit zusammen. Die thermische Abbaubarkeit soll eine potenzielle Bioakkumulation in der Injektionsbohrung und dem Reservoir verhindern. Langzeitlaborversuche in hermetischen Glasampullen und Kurzzeitversuche in Headspace-Vials mit inhibitorversetztem Thermalwasser, die beide ein anaerobes geschlossenes System darstellen, wurden durchgeführt. Die Differenzierung zwischen thermischem und mikrobiellem Abbau erfolgte durch die parallele Präparation von Niedrig- (15 - 25 °C) und Hochtemperaturversuchsreihen (115 °C) sowie dem Einsatz eines Biozids und Sterilfiltration. Die Versuchszeiträume variierten von 16 h bis zu 6 Monaten. Durch die Auswertung mittels Hochleistungsflüssigkeitschromatographie konnte der thermische Abbau innerhalb von Stunden zu einem Zwischenprodukt festgestellt werden, welches nach 3 Wochen vollständig thermisch abgebaut war. Durch den nachgewiesenen thermischen Abbau kann nun eine langfristige Nutzungslizenz der Kraftwerksbetreiber beantragt werden

The impact of sulfur hexafluoride (SF₆) sinks on age of air climatologies and trends

Mean age of air (AoA) is a common diagnostic for the strength of the stratospheric overturning circulation in both climate models and observations. AoA climatologies and AoA trends over the recent decades of model simulations and proxies derived from observations of long-lived tracers do not agree. Satellite observations show much older air than climate models, and while most models compute a clear decrease in AoA over the last decades, a 30-year time series from measurements shows a statistically nonsignificant positive trend in the Northern Hemisphere extratropical middle stratosphere. Measurement-based AoA derivations are often founded on observations of the trace gas sulfur hexafluoride (SF$_{6}$), a fairly long-lived gas with a near-linear increase in emissions during recent decades. However, SF$_{6}$ has chemical sinks in the mesosphere that are not considered in most model studies. In this study, we explicitly compute the chemical SF$_{6}$ sinks based on chemical processes in the global chemistry climate model EMAC (ECHAM/MESSy Atmospheric Chemistry). We show that good agreement between stratospheric AoA in EMAC and MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) is reached through the inclusion of chemical SF$_{6}$ sinks, as these sinks lead to a strong increase in the stratospheric AoA and, therefore, to a better agreement with MIPAS satellite observations. Remaining larger differences at high latitudes are addressed, and possible reasons for these differences are discussed. Subsequently, we demonstrate that the AoA trends are also strongly influenced by the chemical SF6 sinks. Under consideration of the SF$_{6}$ sinks, the AoA trends over the recent decades reverse sign from negative to positive. We conduct sensitivity simulations which reveal that this sign reversal does not result from trends in the stratospheric circulation strength nor from changes in the strength of the SF$_{6}$ sinks. We illustrate that even a constant SF$_{6}$ destruction rate causes a positive trend in the derived AoA, as the amount of depleted SF$_{6}$ scales with increasing SF$_{6}$ abundance itself. In our simulations, this effect overcompensates for the impact of the accelerating stratospheric circulation which naturally decreases AoA. Although various sources of uncertainties cannot be quantified in detail in this study, our results suggest that the inclusion of SF$_{6}$ depletion in models has the potential to reconcile the AoA trends of models and observations. We conclude the study with a first approach towards a correction to account for SF$_{6}$ loss and deduce that a linear correction might be applicable to values of AoA of up to 4 years

Interactions between the calcium scaling inhibitor NC47.1 B, geothermal fluids, and microorganisms – results of in situ monitoring in the Bavarian Molasse Basin (Germany) and accompanying laboratory experiments

Application of the environmentally friendly scaling inhibitor NC47.1 B in geothermal systems was stud- ied in laboratory and field-scale experiments. Biodegradation was investigated under anaerobic, in situ-like conditions and a mass balance confirmed the almost complete conversion of the polycarboxylate to e.g. acetate, formate, methane and CO2. Much higher concentrations of inhibitor were chosen than applied in situ and rapid degradation was observed in biofilm-inoculated setups: A concentration of 100 mg/L of the inhibitor was degraded below detection limit within 8 d of incubation. Furthermore, the inhibitor was applied at the geothermal plant in Unterhaching, Germany. Moni- toring of the microbial community in situ showed an in crease in the abundance of Bacteria. Particularly, relatives of the fermenting Caldicellulosiruptor dominated the biocenosis after about six months of continuous inhibitor dosage (5–10 mg/L). However, in long-term laboratory experiments representatives of Caldicellulosiruptor were only detected in traces and the microbial community comprised a broader spectrum of fermentative bacteria. The different composi- tion of the biocenosis in situ and in laboratory experiments is probably caused by the different inhibitor concentrations, temperatures as well as nutrient availability in situ compared to the closed system of the batch experiments

Exercise hemodynamics of bovine versus porcine bioprostheses: A prospective randomized comparison of the mosaic and perimount aortic valves

ObjectiveThis prospective randomized study compares a porcine with a bovine bioprosthesis in the aortic position with regard to hemodynamic performance during exercise.MethodsBetween August of 2000 and December of 2002, 136 patients underwent aortic valve replacement with the porcine Medtronic Mosaic (n = 66) or the bovine Carpentier-Edwards Perimount (n = 70) bioprosthesis. Transthoracic echocardiography was performed to assess hemodynamic and dimensional data preoperatively and 10 months postoperatively; the latter follow-up included stress echocardiography with treadmill exercise.ResultsAt rest and during exercise (25 and 50 W), there was a significant difference in mean pressure gradient between the bovine and the porcine valves with labeled sizes 21 and 23, with superiority of the Perimount prosthesis. There was no difference in effective orifice area and incidence of patient-prosthesis mismatch among all sizes. The left ventricular mass index decreased significantly within 10 months postoperatively in the size 23 bovine group and the size 25 porcine group.ConclusionsOur data show a significant superiority of pressure gradients for the bovine bioprosthesis, especially with small valve sizes, when compared with the porcine device, which is more distinctive during exercise

Effects of heat shocks on biofilm formation and the influence on corrosion and scaling in a geothermal plant in the North German Basin

At geothermal plants, process failures often occur due to corrosion and scaling processes. Especially after heat extraction, sulfate reducing bacteria contribute to corrosion processes by producing reduced sulfur compounds. In biofilms containing scales such as iron sulfides, corrosion processes are enhanced. In a mobile bypass system located at the geothermal plant in Neubrandenburg (North German Basin), the influence of biofilm formation on corrosion and scaling was investigated. Short-term heat shocks were successfully tested in the bypass system in order to reduce biofilm formation and thus to diminish corrosion and scaling processes

MALEG – Machine Learning for Enhancing Geothermal Energy

To improve the efficiency of geothermal energy production the reinjection temperature has to be reduced. Yet in most cases, the geothermal fluid composition is counteracting this temperature reduction. Whilst pressure relief or cooling, highly mineralised geothermal fluids tend to rise uncontrolled mineral precipitation (scaling). This is a strict limiting factor for the efficient and continuous operation of geothermal power plants. The complex and site-specific hydrochemistry of the fluids complicates the prediction and quantification of scalings using deterministic geochemical models. In the MALEG project, geochemical models are complemented by artificial intelligence, which is trained with hydrochemical data provided by on-site experiments. For this purpose, a demonstrator is built resembling a hardware twin of the geothermal power plant, which is capable of representing the thermodynamic processes in the system. The demonstrator will be connected to the power plant via a bypass to conduct hydrochemical precipitation experiments. Continuous monitoring of fluid and solid samples accompanies the experiments to evaluate potential mineral precipitation. These precipitation processes are dependent on the chemical milieu of the fluid. Changing system parameters such as pressure, temperature, pH, or ion concentration enable the formation of scaling. The application of the demonstrator and the corresponding hydrochemical experiments are planned for three geothermal systems involving different reservoir conditions. The collected and analysed data will set up a diverse hydrochemical database, which will be used to develop the AI-based prediction tool “MALEG”. In addition, a digital twin consisting of deterministic geochemical models will validate the predictions of “MALEG”. Thus, the impact of changes in the fluid chemistry can be predicted more accurately. Evaluating scaling formation will allow optimisation of geothermal power plant operating parameters for improving efficiency, the introduction of cascade utilisation, integration of mineral extraction processes, or cost reduction of routine hydrochemical monitoring