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A membrane assisted process for green hydrogen production from a bioethanol derived feedstock is here developed and evaluated, starting from the conventional Steam Methane Reforming (SMR) process. Such a process is suitable for centralized hydrogen production, and is here analyzed for a large-scale H2 production unit with the capacity of 40.000 Nm3/h. The basic Steam Ethanol Reforming (SER) process scheme is modified in a membrane assisted process by integrating the Pd-membrane separation steps in the most suitable reaction steps. The membrane assisted process, configured in three alternative architectures (Open architecture, Membrane Reactor and Hybrid architecture) was evaluated in terms of efficiencies and hydrogen yields, obtaining a clear indication of improved process performance. The alternative membrane assisted process architectures are compared to the basic SER process and to the benchmark SMR process fed by natural gas, for an overall comparative assessment of the efficiency and specific CO2 emissions and for an economic analysis based on the operating expenditures.

The present study questions the sensitivity and the accuracy of Raman spectroscopy as a tool for determining the maturity of natural organic matter (NOM). It focuses on the definition of optimized experimental parameters in order to maximize the quality of the Raman signal and control the accuracy and reproducibility of measurements. A series of 11 coals has been investigated, sampling a wide maturity range (2-7% vitrinite reflectance VR). The role of experimental parameters is first investigated. An excitation wavelength of 514.5 nm gives better results than 457.9 and 632.8 nm, minimizing the fluorescence background observed in the spectra of low-rank coals. Both Raman and fluorescence spectra were investigated with time-resolved experiments in air and argon. These data show that fluorescence and Raman spectra are sensitive to acquisition time and laser power parameters, and reveal a physicochemical instability of the samples under laser irradiation, mostly due to photo-oxidation processes. These data clearly show that the experiments, especially in air, should be performed with strictly constant acquisition parameters. In addition, the results of a whole series of coal measurements performed in air under constant experimental conditions show that Raman spectroscopy is definitely sensitive to the maturity of coal samples with VR> approximately 1%. The most sensitive spectral maturity tracers are the width of the D-band (FWHM-D), the ratio of the peak intensities of the D- and G-bands (I(D)/I(G)), the normalized ratio of the band integrated intensities A(D)/[A(D)+A(G)] for the maturity range VR=3-7% and the width of the G-band (FWHM-G) for VR=1-5%. However, the accuracy and reproducibility are definitely weaker in such measurements compared to the standard VR. Future work must solve the problem of sample stability under laser irradiation, and greatly increase the number of samples to improve the statistical significance of the results.

Abstract This study presents a detailed kinetic investigation into ultra-rich oxidation of H 2 S-CH 4 under high temperature (900–1250 °C) and ambient pressure. Effects of temperature, initial H 2 S/CH 4 ratio and equivalence ratio (Φ) on reactants conversions and products distributions were experimentally studied in a tubular flow reactor and kinetically analyzed by CHEMKIN software. A detailed kinetic mechanism involving 85 species and 515 reactions has been developed and validated using reference data for H 2 S-CH 4 decomposition and results from extended experimental conditions involving the O 2 addition. For H 2 S-CH 4 system, conversion of H 2 S increased steady with the rising temperature while reactivity of CH 4 was weak at temperature below 1000 °C. At temperature higher than 1000 °C, conversion of CH 4 increased rapidly and devoted further formation of H 2 and CS 2 mainly via reacting with H 2 S decomposition products. The H 2 production efficiency was negatively associated with initial H 2 S fraction as H 2 S decomposition was dominant H 2 source within 1150 °C. The stoichiometric ratio for H 2 S/CH 4 merely showed its advantage in H 2 production at higher temperature under which CH 4 reached its equilibrium conversion swiftly. Introduction of little amount of O 2 (Φ = 6 or higher) accelerated the whole reaction process and triggered H 2 S partial oxidation and H 2 formation at lower temperature. CH 4 explicitly showed inferior position in oxidation competition with H 2 S and maintained poor conversion at temperature below 950 °C. The results of rate of production (ROP) analysis at condition without O 2 showed that CH 4 reactivity showed dependence on free S radical via S + CH 4 = SH + CH 3 , and the formed CH 3 was mainly converted via reacting with SH and H radicals. CH 3 could be concurrently reverted to CH 4 via reactions with H 2 S and H 2 . O 2 activated the whole system by forming chain branching radicals O and OH. These radicals promoted H 2 S and CH 4 conversions to form richer S, H and CH 3 radicals. SH + CS = CS 2 + H was important for CS 2 formation and with presence of O 2 , CS 2 was likely to be consumed via oxidation reactions. Finally reaction pathways for H 2 S, CH 4 conversion and H 2 , CS 2 formation were presented.

The synthesis of biodiesel from Jatropha curcas by transesterification is kinetically controlled. It depends on the molar ratio, reaction time, and temperature, as well as the catalyst nature and quantity. The aim of this study was to explore the transesterification of low-cost, inedible J. curcas seed oil utilizing both homogenous (potassium hydroxide; KOH) and heterogenous (calcium oxide; CaO) catalysis. In this effort, two steps were used. First, free fatty acids in J. curcas oil were reduced from 12.4 to less than 1 wt.% with sulfuric acid-catalyzed pretreatment. Transesterification subsequently converted the oil to biodiesel. The yield of fatty acid methyl esters was optimized by varying the reaction time, catalyst load, and methanol-to-oil molar ratio. A maximum yield of 96% was obtained from CaO nanoparticles at a reaction time of 5.5 h with 4 wt.% of the catalyst and an 18:1 methanol-to-oil molar ratio. The optimum conditions for KOH were a molar ratio of methanol to oil of 9:1, 5 wt.% of the catalyst, and a reaction time of 3.5 h, and this returned a yield of 92%. The fuel properties of the optimized biodiesel were within the limits specified in ASTM D6751, the American biodiesel standard. In addition, the 5% blends in petroleum diesel were within the ranges prescribed in ASTM D975, the American diesel fuel standard.

Uncontaminated and As-contaminated fronds of Pteris vittata L., an As-hyperaccumulator fern used to phytoextract As from contaminated soils and water, were converted by sub-critical water (300 °C, 25 Pa) and supercritical water (400 °C, 25 Pa) treatments. Frond biomass was reduced between 70 and 77%. Compared to sub-critical conditions, supercritical conditions decreased C and inorganic contents in both the solid and liquid phases for uncontaminated and contaminated fronds and promoted CH4 formation. Higher As, Fe and Zn contents in contaminated fronds promoted decreasing C contents and the formations of cyclopentenones and benzenediols in the liquid phase. Al, Fe, P, Zn and Ca mainly remained in the solid phase whereas As and S were transferred to the liquid phase for both phytomasses. As the temperature increased from 300 °C to 400 °C, the concentrations of cyclopentenones and phenols in the liquid phase rose while those of guaiacols and other compounds decreased for both phytomasses. Arsenic in the liquid phase was removed by sorption on hydrous iron oxide.

Coalbed methane (CBM) resources cannot be efficiently explored and exploited without a robust understanding of the permeability of fracture-size heterogeneities in coal. In this study, two sister coal samples were imparted with pre-developed cleat and connected fractures, and the permeability of the coal samples was measured under different conditions of controlled confining and gas pressures. Furthermore, the implications of the results for CBM exploration and exploitation were discussed. The permeability of coal with cleat development ranged from 0.001–0.01 mD, indicating ultra-low permeability coal. The gas migration in this coal changed from a linear flow to a non-linear flow, with the increase in gas pressure (>1 MPa). Thus, the permeability of the coal initially increased and then decreased. However, the Klinkenberg effect does not exist in this ultralow-permeability coal. For the coal sample with connected fracture, permeability ranged from 0.1–10 mD, which is larger by hundred orders of magnitude than that of the sample with cleat. For this coal, with a decrease in gas pressure (<1 MPa), the Klinkenberg effect significantly increased the permeability of the coal. With an increase in the applied confining pressure, both the Klinkenberg coefficient and permeability of the coal presented a decreasing trend. It is suggested that field fracture investigation is a prerequisite and indispensable step for successful CBM production. The coal beds that cleat network is well conductive to the connected fracture can be an improved target area for CBM production. During CBM production, a variety of flow regimes are available owing to the decrease in CBM reservoir pressure. In particular, under the low CBM reservoir pressure and low in situ geo-stress conditions, the gas migration in the CBM reservoir with connected facture development exhibits remarkable free-molecular flow. Thus, the reservoir permeability and predicted CBM production will be enhanced.

Summary Carbon dioxide (CO2) foam has been widely studied in connection with its application in enhanced oil recovery (EOR). This paper reports an experimental study concerning CO2 foam propagation in a surfactant-saturated Bentheim sandstone core and the subsequent liquid injection with the aid of X-ray computed tomography (CT). The experiments were carried out under various system backpressures. It is found that CO2 foam flows in a characteristic front-like manner in the transient stage and that the water saturation keeps at relatively high level at the outlet of the porous media because of CO2 solubility and capillary end effect. The subsequent surfactant solution injection shows a significant fingering behavior, accompanied by a low flow resistance over the core. It is also found that CO2 foam flow shows higher liquid saturation near the outlet and lower pressure drops under higher system backpressures. This can be attributed to the solubility of CO2 in the liquid phase. The results indicate the advantage of using foam in EOR processes such as water alternating foam (WAF), in which foam flow has higher sweep efficiency and stronger mobility control ability compared, for instance, to water alternating gas (WAG). Nevertheless, care should be taken during the water-injection stage in order not to favor the fingering.