Low temperature reforming of biogas over K-, Mg- and Ce-promoted Ni/Al₂O₃ catalysts for the production of hydrogen rich syngas: Understanding the plasma-catalytic synergy

Plasma-catalytic biogas reforming over Ni-X/Al2O3 catalyst (X = K, Mg and Ce) has been carried out in a coaxial dielectric barrier discharge (DBD) plasma reactor at 160 °C. Three different process modes: plasma-alone, catalysis-alone and plasma-catalysis have been investigated to get new insights into the synergistic effect resulted from the interaction of the plasma with the promoted Ni catalysts. Compared to the biogas reforming using either plasma-alone or catalysis-alone mode at the same temperature (160 °C), the combination of the plasma with the Ni-based catalysts exhibited a low temperature synergistic effect, as evidenced from the much higher reforming performance of the plasma-catalytic process compared to that of the sum of the individual processes (plasma-alone and catalysis-alone). The addition of promoters (K, Mg and Ce) into the Ni/Al2O3 catalyst enhanced the conversion of CH4, the yield of H2 and the energy efficiency of the plasma process. In this study, the behaviour of K, Mg and Ce promoters in the low temperature plasma-catalytic biogas reforming was clearly different from that in high temperature thermal catalytic process in terms of the conversion of CH4 and carbon deposition, which could be ascribed to the temperature-dependent character of the promotors. In the plasma-catalytic biogas reforming, the Ni-K/Al2O3 catalyst showed the best performance, enhancing the conversion of both CO2 and CH4, the yield of H2, CO and C2–C4 alkanes and the energy efficiency of the plasma process. The highest conversion of CO2 (22.8%) and CH4 (31.6%) was achieved by placing the K-promoted catalyst in the plasma reforming process. The Mg-promoted catalyst remarkably increased the H2/CO molar ratio in the gas products (up to 2.2) due to the decreased CO2 conversion. In addition, compared to the un-promoted Ni/Al2O3 catalyst, although the use of the promoted catalysts increased the carbon deposition on the surface of the spent catalysts by 22%–26%, the total amount of deposited carbon was still less than that reported in high temperature catalytic dry reforming processes. More than 80% of the increased carbonaceous species was in the form of reactive carbon species, which can be easily oxidized by CO2 and O atoms and maintain the stability of the catalysts during the reforming reaction.</p

Direct conversion of methanol to n-C4H10 and H-2 in a dielectric barrier discharge reactor

Methanol is an important H-carrier and C1 chemical feedstock. In this paper, a direct conversion of methanol to n-C4H10 and H2 was achieved for the first time in a dielectric barrier discharge (DBD) non-thermal plasma reactor. The selective formation of n-C4H10 by limiting COx (x = 1 and 2) generation was obtained by optimizing different plasma processing parameters including the methanol inlet concentration, discharge power, and pre-heating temperature. The results showed that a higher methanol inlet concentration and a higher pre-heating temperature favors the formation of n-C4H10, while a higher methanol inlet concentration and a lower discharge power can effectively limit the formation of CO. The optimal selectivity for n-C4H10 (37.5%), H2 (28.9%) and CO (14%) was achieved, with a methanol conversion of 40.0%, at a methanol inlet concentration of 18 mol%, a discharge power of 30 W and a pre-heating temperature of 140 °C using N2 as a carrier gas. Value-added liquid chemicals (e.g., alcohols, acids, and heavy hydrocarbons) were also obtained from this reaction. Emission spectroscopy diagnostics reveals the formation of various reactive species (e.g., CH, C2, CN, H and metastable N2) in the CH3OH/N2 DBD. Possible reaction pathways for the formation of n-C4H10 were proposed and discussed

Bounds of Efficiency at Maximum Power for Normal-, Sub- and Super-Dissipative Carnot-Like Heat Engines

The Carnot-like heat engines are classified into three types (normal-, sub- and super-dissipative) according to relations between the minimum irreversible entropy production in the "isothermal" processes and the time for completing those processes. The efficiencies at maximum power of normal-, sub- and super-dissipative Carnot-like heat engines are proved to be bounded between $\eta_C/2$ and $\eta_C/(2-\eta_C)$, $\eta_C /2$ and $\eta_C$, 0 and $\eta_C/(2-\eta_C)$, respectively. These bounds are also shared by linear, sub- and super-linear irreversible Carnot-like engines [Tu and Wang, Europhys. Lett. 98, 40001 (2012)] although the dissipative engines and the irreversible ones are inequivalent to each other.Comment: 1 figur

Phonon anomaly in BaFe2As2

The detailed optical properties of BaFe2As2 have been determined over a wide frequency range above and below the structural and magnetic transition at T_N = 138 K. A prominent in-plane infrared-active mode is observed at 253 cm^{-1} (31.4 meV) at 295 K. The frequency of this vibration shifts discontinuously at T_N; for T < T_N the frequency of this mode displays almost no temperature dependence, yet it nearly doubles in intensity. This anomalous behavior appears to be a consequence of orbital ordering in the Fe-As layers.Comment: 4 pages, 3 figures and one table (minor revisions

An improvement of isochronous mass spectrometry: Velocity measurements using two time-of-flight detectors

Isochronous mass spectrometry (IMS) in storage rings is a powerful tool for mass measurements of exotic nuclei with very short half-lives down to several tens of microseconds, using a multicomponent secondary beam separated in-flight without cooling. However, the inevitable momentum spread of secondary ions limits the precision of nuclear masses determined by using IMS. Therefore, the momentum measurement in addition to the revolution period of stored ions is crucial to reduce the influence of the momentum spread on the standard deviation of the revolution period, which would lead to a much improved mass resolving power of IMS. One of the proposals to upgrade IMS is that the velocity of secondary ions could be directly measured by using two time-of-flight (double TOF) detectors installed in a straight section of a storage ring. In this paper, we outline the principle of IMS with double TOF detectors and the method to correct the momentum spread of stored ions.Comment: Accepted by Nuclear Inst. and Methods in Physics Research,

Spin 3/2 dimer model

We present a parent Hamiltonian for weakly dimerized valence bond solid states for arbitrary half-integral S. While the model reduces for S=1/2 to the Majumdar-Ghosh Hamiltonian we discuss this model and its properties for S=3/2. Its degenerate ground state is the most popular toy model state for discussing dimerization in spin 3/2 chains. In particular, it describes the impurity induced dimer phase in Cr8Ni as proposed recently. We point out that the explicit construction of the Hamiltonian and its main features apply to arbitrary half-integral spin S.Comment: 5+ pages, 6 figures; to appear in Europhysics Letter