Optimisation of Propane Production from Hydrothermal Decarboxylation of Butyric Acid Using Pt/C Catalyst: Influence of Gaseous Reaction Atmospheres

The displacement and eventual replacement of fossil-derived fuel gases with biomass-derived alternatives can help the energy sector to achieve net zero by 2050. Decarboxylation of butyric acid, which can be obtained from biomass, can produce high yields of propane, a component of liquefied petroleum gases. The use of different gaseous reaction atmospheres of nitrogen, hydrogen, and compressed air during the catalytic hydrothermal conversion of butyric acid to propane have been investigated in a batch reactor within a temperature range of 200–350 °C. The experimental results were statistically evaluated to find the optimum conditions to produce propane via decarboxylation while minimizing other potential side reactions. The results revealed that nitrogen gas was the most appropriate atmosphere to control propane production under the test conditions between 250 °C and 300 °C, during which the highest hydrocarbon selectivity for propane of up to 97% was achieved. Below this temperature range, butyric acid conversion remained low under the three reaction atmospheres. Above 300 °C, competing reactions became more significant. Under compressed air atmosphere, oxidation to CO2 became dominant, and under nitrogen, thermal cracking of propane became significant, producing both ethane and methane as side products. Interestingly, under a hydrogen atmosphere, hydrogenolytic cracking propane became dominant, leading to multiple C–C bond cleavages to produce methane as the main side product at 350 °C.

Improved Bio-Oil Quality from Pyrolysis of Pine Biomass in Pressurized Hydrogen

The pyrolysis of pine sawdust was carried out in a fixed bed reactor heated from 30 °C to a maximum of 700 °C in atmospheric nitrogen and pressurized hydrogen (5 MPa). The yield, elemental composition, thermal stability, and composition of the two pyrolysis bio-oils were analyzed and compared. The result shows that the oxygen content of the bio-oil (17.16%) obtained under the hydrogen atmosphere was lower while the heating value (31.40 MJ/kg) was higher than those of bio-oil produced under nitrogen atmosphere. Compounds with a boiling point of less than 200 °C account for 63.21% in the bio-oil at pressurized hydrogen atmosphere, with a proportion 14.69% higher than that of bio-oil at nitrogen atmosphere. Furthermore, the hydrogenation promoted the formation of ethyl hexadecanoate (peak area percentage 19.1%) and ethyl octadecanoate (peak area percentage 15.42%) in the bio-oil. Overall, high pressure of hydrogen improved the bio-oil quality derived from the pyrolysis of pine biomass.

Chemical synthesis of nanostructured magnetic hardened alloy of the Nd-Fe-B system

Hard magnetic nanopowders of the Nd15Fe78B7 alloy were synthesized from mixtures of Nd, Fe and Fe-B oxides with CaH2 in a hydrogen atmosphere at 800 °C by a reduction-diffusion process. Nd, Fe, Fe-B oxides were synthesized by chemical deposition. The resulting particles had a granular shape with an average size: Nd2O3 — 50 nm, Fe2O3 — 95 nm, Fe3BO6 — 57 nm. The particle size of the Nd15Fe78B7 alloy was 45–140 nm. It is shown that the proposed method is suitable for obtaining nanopowders of hard magnetic alloys of the Nd-Fe-B system.

Influence of Hydrogenation on Morphology, Chemical Structure and Photocatalytic Efficiency of Graphitic Carbon Nitride

In this contribution, the effect of hydrogenation conditions atmosphere (temperature and time) on physicochemical properties and photocatalytic efficiency of graphitic carbon nitride (g-C3N4, gCN) was studied in great details. The changes in the morphology, chemical structure, optical and electrochemical properties were carefully investigated. Interestingly, the as-modified samples exhibited boosted photocatalytic degradation of Rhodamine B (RhB) with the assistance of visible light irradiation. Among modified gCN, the sample annealed at 500 °C for 4 h (500-4) in H2 atmosphere exhibited the highest photocatalytic activity—1.76 times higher compared to pristine gCN. Additionally, this sample presented high stability and durability after four cycles. It was noticed that treating gCN with hydrogen at elevated temperatures caused the creation of nitrogen vacancies on gCN surfaces acting as highly active sites enhancing the specific surface area and improving the mobility of photogenerated charge carriers leading to accelerating the photocatalytic activity. Therefore, it is believed that detailed optimization of thermal treatment in a hydrogen atmosphere is a facile approach to boost the photoactivity of gCN.

A Comparison of the Efficiency of Catalysts Based on Ni, Ni-Co and Ni-Mo in Pressure Pyrolysis of Biomass Leading to Hythane

A thermal conversion of biomass to hythane using catalysts was studied. Low-temperature pyrolysis of two different types of biomass was performed in a pressure sealed reactor, and the resulting gas with high contents of CO2 and CO was methanized in a hydrogen atmosphere at a pressure of 30 bar. As catalysts, Ni/Al2O3, NiCo/Al2O3 and NiMo/Al2O3 were used and their catalytic activity was evaluated. The NiCo/Al2O3 catalyst showed the highest catalytic activity, Ni/Al2O3 had a lower but comparable one, and NiMo/Al2O3 showed the lowest activity. The resulting hythane contained 70 vol.% CH4 and 10 vol.% H2 (with NiCo/Al2O3 catalyst, HHV 29.20 MJ/m3, LHV 26.32 MJ/m3), or 57 vol.% CH4 and 23 vol% H2 (with Ni/Al2O3, HHV 25.92 MJ/m3, LHV 23.21 MJ/m3) or 47 vol.% CH4 and 27 vol.% H2 (with NiMo/Al2O3, HHV 23.23 MJ/m3, LHV 20.76 MJ/m3). It has been found that secondary reactions of volatile biomass products are of great importance for successful pressure pyrolysis.

NICER Study of Pulsed Thermal X-Rays from Calvera: A Neutron Star Born in the Galactic Halo?

Calvera (1RXS J141256.0+792204) is an isolated neutron star detected only through its thermal X-ray emission. Its location at high Galactic latitude (b = +37°) is unusual if Calvera is a relatively young pulsar, as suggested by its spin period (59 ms) and period derivative (3.2 × 10−15 s s−1). Using the Neutron Star Interior Composition Explorer, we obtained a phase-connected timing solution spanning four years, which allowed us to measure the second derivative of the frequency ν ̈ = − 2.5 × 10 − 23 Hz s−2 and to reveal timing noise consistent with that of normal radio pulsars. A magnetized hydrogen atmosphere model, covering the entire star surface, provides a good description of the phase-resolved spectra and energy-dependent pulsed fraction. However, we found that a temperature map more anisotropic than that produced by a dipole field is required, with a hotter zone concentrated toward the poles. By adding two small polar caps, we found that the surface effective temperature and that of the caps are ∼0.1 and ∼0.36 keV, respectively. The inferred distance is ∼3.3 kpc. We confirmed the presence of an absorption line at 0.7 keV associated with the emission from the whole star surface, difficult to interpret as a cyclotron feature and more likely originating from atomic transitions. We searched for pulsed γ-ray emission by folding seven years of Fermi-LAT data using the X-ray ephemeris, but no evidence for pulsations was found. Our results favor the hypothesis that Calvera is a normal rotation-powered pulsar, with the only peculiarity of being born at a large height above the Galactic disk.

Preliminary Study of the Rhenium Addition on the Structure and Mechanical Properties of Tungsten Heavy Alloy

The results of structure and mechanical property investigations of tungsten heavy alloy (THA) with small additions of rhenium powder are presented. The material for the study was prepared using liquid phase sintering (LPS) of mixed and compacted powders in a hydrogen atmosphere. From the specimens, the samples for mechanical testing and structure investigations were prepared. It follows from the results of the microstructure observations and mechanical studies, that the addition of rhenium led to tungsten grain size decreasing and influencing the mechanical properties of W-Ni-Fe-Co base heavy alloy.

CCD Time-Series Photometry of White Dwarf Stars

<p>This thesis describes a practical programme that focused on CCD photometry of pulsating white dwarf (WD) stars. The first part of this thesis describes the development of two high-speed CCD photometer instruments and their data reduction pipeline, while the remainder describes the observation and analysis of several pulsating WDs and other targets. The two photometers (Puoko-nui North and South) share a common hardware design that is optimized for acquiring efficient photometry with integration periods of milliseconds through to minutes. The design integrates a commercial CCD (Charge-Coupled Device) camera and GPS (Global Positioning System) receiver with custom timing electronics and control software. The reduction and visualization software developed for these instruments provide detailed real-time information to the observer, and a streamlined data reduction pipeline. EC04207-4748 is a pulsating helium atmosphere WD that shows significant non-sinusoidal intensity variations. We show that the pulsation spectrum of this WD can be described by four independent pulsation eigenmodes plus linear combinations that arise from non-linear energy transport through a sub-surface convection layer. Our results are consistent with similar analyses that have been made for similar stars, and add an additional data point to the growing catalogue of these convection measurements. We argue that the convection layer depth may form a useful substitute for the effective temperatures of these WDs. GWLibrae is the class prototype of the accreting WD pulsators. These stars exist in cataclysmic variable (CV) systems, and show a mix of CV and pulsating WD-related phenomena. Our observations of GW Librae four - six years after its 2007 outburst show signs of quasi-stable intensity modulations that we believe may be caused by non-radial pulsations, but these are not convincingly explained by existing WD or CV models. L19-2 is a hydrogen atmosphere WD pulsator that shows extremely stable pulsation behaviour. We combine new observations with archival observations dating back to the mid 1970's, and derive a preliminary estimate of the period rate of change Ṗ for two of the pulsation modes in this target. We show a clear result for the main 192 s pulsation mode Ṗf₂ ≾ 10⁻¹⁴ s s-¹, and discuss the improvements that we plan to make in order to convincingly improve this constraint by an additional order of magnitude. Observations of other rapidly variable targets include two extremely low mass (ELM) WDs, which exhibit variability due to their orbital motion (J0751) as well as non-radial pulsations (J1518); the 33 ms optical period of the Crab Pulsar; the helium atmosphere WD pulsators EC05221-4725 and EC20058-5234; the stable hydrogen atmosphere pulsator G117–B15A; and the eclipsing sdB binary system PG1336-018.</p>