•Insights into power requirements of biomethane production from biogas are provided.•Process model is constructed, validated and simulated.•High-pressure and low-pressure plant operation in different ...configurations is compared.
Biogas upgrading by water scrubbing followed by biomethane compression is an environmentally benign process. It may be achieved using various plant configurations characterised by various power requirements with associated effects on biomethane sustainability. Therefore, the current study has been undertaken to systematically investigate the power requirements of a range of water scrubbing options. Two groups of water scrubbing are analysed: (1) high pressure water scrubbing (HPWS) and (2) near-atmospheric pressure water scrubbing (NAPWS). A water scrubbing plant model is constructed, experimentally validated and simulated for seven upgrading plant configurations. Simulation results show that the power requirement of biogas upgrading in HPWS plants is mainly associated with biogas compression. In contrast, in NAPWS plants the main power is required for water pumping. In both plants the compression of the biomethane from atmosphereic pressure to 20MPa also contributes remarkably. It is observed that the lowest specific power requirement can be obtained for a NAPWS plant without water regeneration (0.24kWh/Nm3 raw biogas) but this plant requires cheap water supply, e.g. outlet water from a sewage treatment plant or river. The second is HPWS without flash (0.29kWh/Nm3 raw biogas). All other HPWS with flash and NAPWS with water regeneration plants have specific power requirements between 0.30 and 0.33kWh/Nm3 raw biogas. Biogas compression without upgrading requires about 0.29kWh/Nm3 raw biogas. The thermodynamic efficiency of biogas upgrading is between 2.2% and 9.8% depending on the plant configuration while biomethane compression efficiency is higher, about 55%. This result implies that the upgrading process has a remarkable potential for improvement whereas compression is very close to its thermodynamic limit. The potential for minimising energy dissipation in the state-of-the-art HPWS upgrading plant with flash by applying a rotary hydraulic pumping device is evaluated at about 0.036kWh/Nm3 raw biogas meaning the specific power requirement reduction of 10%.
Mechanical and physicochemical treatments of milk induce structural modifications of the casein (CN) micelles, affecting their techno-functional properties in dairy processing. Here, we studied the ...effect of alkalinization and ultra-high-pressure homogenization (UHPH) on CN micelles in raw skim milk (rSM) and pasteurized skim milk (pSM). The pH of both skim milks (approximately 6.7) was adjusted to 8.5 and 10.5 before UHPH at 100, 200, and 300 MPa. The structural changes of the CN micelles during the treatments were assessed using laser diffraction, transmission electron microscopy, and turbidity measurements. Finally, ultracentrifugation (70,000 × g for 1 h at 20°C) was carried out to evaluate the protein's distribution between the supernatant (serum phase) and the pellet (colloidal phase) by gel electrophoresis and protein concentration measurement. Alkalinization of both skim milks induced a significant reduction in turbidity, whereas an increase of the average particle size was observed, the effect being more severe in pSM than rSM. At alkaline pH, more proteins were recovered in the serum phase, which suggested that the CN underwent major rearrangements into nonsedimentable CN forms of various sizes, as confirmed by transmission electron microscopy. The amount of CN found in the serum phase at pH 8.5 also increased with the UHPH pressure. Although UHPH did not influence the average CN micelle size at pH 6.7 and 8.5, a pressure-dependent decrease was observed at pH 10.5 for both skim milks. The structural changes of the CN micelles observed in this study throughout the combination of alkalinization and UHPH could be of interest for developing new dairy ingredients with improved functionality.
The many-body quantum nature of molecules determines their static and dynamic properties, but remains the main obstacle in their accurate description. Ultrashort extreme ultraviolet pulses offer a ...means to reveal molecular dynamics at ultrashort timescales. Here, we report the use of time-resolved electron-momentum imaging combined with extreme ultraviolet attosecond pulses to study highly excited organic molecules. We measure relaxation timescales that increase with the state energy. High-level quantum calculations show these dynamics are intrinsic to the time-dependent many-body molecular wavefunction, in which multi-electronic and non-Born-Oppenheimer effects are fully entangled. Hints of coherent vibronic dynamics, which persist despite the molecular complexity and high-energy excitation, are also observed. These results offer opportunities to understand the molecular dynamics of highly excited species involved in radiation damage and astrochemistry, and the role of quantum mechanical effects in these contexts.
Context.
The interaction of polycyclic aromatic hydrocarbons (PAHs) with vacuum ultraviolet (VUV) photons triggers the emission of the well-known aromatic infrared bands (AIBs), but other mechanisms, ...such as fragmentation, can be involved in this interaction. Fragmentation leads to selection effects that favor specific sizes and structures.
Aims.
Our aim is to investigate the impact of aliphatic bonds on the VUV photostability of PAH cations in a cryogenic and collisionless environment with conditions applicable for photodissociation regions (PDRs).
Methods.
The studied species are derived from pyrene (C
16
H
10
) and coronene (C
24
H
12
) and contain aliphatic bonds either in the form of methyl or ethyl sidegroups or of superhydrogenation. Their cations are produced by laser desorption ionization and isolated in the cryogenic ion cell of the PIRENEA setup, where they are submitted to VUV photons of 10.5 eV energy over long timescales (~1000 s). The parent and fragment ions are mass-analyzed and their relative intensities are recorded as a function of the irradiation time. The fragmentation cascades are analyzed with a simple kinetics model from which we identify fragmentation pathways and derive fragmentation rates and branching ratios for both the parents and their main fragments.
Results.
Aliphatic PAH derivatives are found to have a higher fragmentation rate and a higher carbon to hydrogen loss compared to regular PAHs. On the other hand, the fragmentation of PAHs with alkylated sidegroups forms species with peripheral pentagonal cycles, which can be as stable as, or even more stable than, the bare PAH cations. This stability is quantified for the main ions involved in the fragmentation cascades by the comparison of the fragmentation rates with the photoabsorption rates derived from theoretical photoabsorption cross sections. The most stable species for which there is an effective competition of fragmentation with isomerization and radiative cooling are identified, providing clues on the structures favored in PDRs.
Conclusions.
This work supports a scenario in which the evaporation of nanograins with a mixed aliphatic and aromatic composition followed by VUV photoprocessing results in both the production of the carriers of the 3.4 μm AIB by methyl sidegroups and in an abundant source of small hydrocarbons at the border of PDRs. An additional side effect is the efficient formation of stable PAHs that contain some peripheral pentagonal rings. Our experiments also support the role of isomerization processes in PAH photofragmentation, including the H-migration process, which could lead to an additional contribution to the 3.4 μm AIB.
Hole migration is a fascinating process driven by electron correlation, in which purely electronic dynamics occur on a very short time scale in complex ionized molecules, prior to the onset of ...nuclear motion. However, it is expected that due to coupling to the nuclear dynamics, these oscillations will be rapidly damped and smeared out, which makes experimental observation of the hole migration process rather difficult. In this Letter, we demonstrate that the instantaneous ionization of benzene molecules initiates an ultrafast hole migration characterized by a periodic breathing of the hole density between the carbon ring and surrounding hydrogen atoms on a subfemtosecond time scale. We show that these oscillations survive the dephasing introduced by the nuclear motion for a long enough time to allow their observation. We argue that this offers an ideal benchmark for studying the influence of hole migration on molecular reactivity.
Haumea-one of the four known trans-Neptunian dwarf planets-is a very elongated and rapidly rotating body. In contrast to other dwarf planets, its size, shape, albedo and density are not well ...constrained. The Centaur Chariklo was the first body other than a giant planet known to have a ring system, and the Centaur Chiron was later found to possess something similar to Chariklo's rings. Here we report observations from multiple Earth-based observatories of Haumea passing in front of a distant star (a multi-chord stellar occultation). Secondary events observed around the main body of Haumea are consistent with the presence of a ring with an opacity of 0.5, width of 70 kilometres and radius of about 2,287 kilometres. The ring is coplanar with both Haumea's equator and the orbit of its satellite Hi'iaka. The radius of the ring places it close to the 3:1 mean-motion resonance with Haumea's spin period-that is, Haumea rotates three times on its axis in the time that a ring particle completes one revolution. The occultation by the main body provides an instantaneous elliptical projected shape with axes of about 1,704 kilometres and 1,138 kilometres. Combined with rotational light curves, the occultation constrains the three-dimensional orientation of Haumea and its triaxial shape, which is inconsistent with a homogeneous body in hydrostatic equilibrium. Haumea's largest axis is at least 2,322 kilometres, larger than previously thought, implying an upper limit for its density of 1,885 kilograms per cubic metre and a geometric albedo of 0.51, both smaller than previous estimates. In addition, this estimate of the density of Haumea is closer to that of Pluto than are previous estimates, in line with expectations. No global nitrogen- or methane-dominated atmosphere was detected.
Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ...ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10(-15) s) and even attosecond (as) (1 as=10(-18) s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.
Context.
Until recently, the 3D shape, and therefore density (when combining the volume estimate with available mass estimates), and surface topography of the vast majority of the largest (
D
≥ 100 ...km) main-belt asteroids have remained poorly constrained. The improved capabilities of the SPHERE/ZIMPOL instrument have opened new doors into ground-based asteroid exploration.
Aims.
To constrain the formation and evolution of a representative sample of large asteroids, we conducted a high-angular-resolution imaging survey of 42 large main-belt asteroids with VLT/SPHERE/ZIMPOL. Our asteroid sample comprises 39 bodies with
D
≥ 100 km and in particular most
D
≥ 200 km main-belt asteroids (20/23). Furthermore, it nicely reflects the compositional diversity present in the main belt as the sampled bodies belong to the following taxonomic classes: A, B, C, Ch/Cgh, E/M/X, K, P/T, S, and V.
Methods.
The SPHERE/ZIMPOL images were first used to reconstruct the 3D shape of all targets with both the ADAM and MPCD reconstruction methods. We subsequently performed a detailed shape analysis and constrained the density of each target using available mass estimates including our own mass estimates in the case of multiple systems.
Results.
The analysis of the reconstructed shapes allowed us to identify two families of objects as a function of their diameters, namely “spherical” and “elongated” bodies. A difference in rotation period appears to be the main origin of this bimodality. In addition, all but one object (216 Kleopatra) are located along the Maclaurin sequence with large volatile-rich bodies being the closest to the latter. Our results further reveal that the primaries of most multiple systems possess a rotation period of shorter than 6 h and an elongated shape (
c
∕
a
≤ 0.65). Densities in our sample range from ~1.3 g cm
−3
(87 Sylvia) to ~4.3 g cm
−3
(22 Kalliope). Furthermore, the density distribution appears to be strongly bimodal with volatile-poor (
ρ
≥ 2.7 g cm
−3
) and volatile-rich (
ρ
≤ 2.2 g cm
−3
) bodies. Finally, our survey along with previous observations provides evidence in support of the possibility that some C-complex bodies could be intrinsically related to IDP-like P- and D-type asteroids, representing different layers of a same body (C: core; P/D: outer shell). We therefore propose that P/ D-types and some C-types may have the same origin in the primordial trans-Neptunian disk.
Abstract
In recent years, there appeared a need for astronomical observations timed with submillisecond accuracy. These include, e.g., timing stellar occultations by small, subkilometer, or fast ...near-Earth asteroids and tracking artificial satellites in low-Earth orbit using optical sensors. Precise astrometry of fast-moving satellites and accurate timing of stellar occultations have parallel needs, requiring a reliable time source and good knowledge of camera delays. Thus, there is a need for an external device that would enable equipment and camera testing to check if they reach the required accuracy in time. We designed, constructed, and thoroughly tested a New EXposure Timing Analyser (NEXTA), a Global Navigation Satellite System–based precise timer allowing us to reach an accuracy of 0.1 ms, which is an order of magnitude better than in previously available tools. The device is a simple strip of blinking diodes to be imaged with a camera and compare the imaged time with the internal camera time stamp. Our tests spanned a range of scientific cameras widely used for stellar occultations and ground-based satellite tracking. The results revealed high reliability of both NEXTA and most of the tested cameras but also pointed out that practically all cameras had internal time biases of various levels. NEXTA can serve the community, being easily reproducible with inexpensive components. We provide all the necessary schemes and usage instructions.
Unraveling ultrafast molecular processes initiated by energetic radiation provides direct information on the chemical evolution under extreme conditions. A prominent example is interstellar media ...where complex molecules such as polycyclic aromatic hydrocarbons (PAHs) are excited by energetic photons. Until recently, ultrafast dynamics following such excitations remained largely unexplored due to the lack of relevant technologies. Here, we use time-resolved mass spectrometry combining ultrashort femtosecond XUV and IR pulses, to investigate the dynamics induced by high-energy photon excitation in PAHs. We demonstrate that excited cations relax through a progressive loss of vibrational selectivity, created at the early-stage dynamics, and which represents the first steps of a complete intramolecular vibrational energy redistribution. This process is in competition with the recently revealed correlation-band dynamics. These results might have direct consequences for the development of XUV molecular physics and other fields such as astrochemistry.
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