Economic assessment of clean hydrogen production from fossil fuels in the intermountain-west region, USA
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Highlights: • A life cycle assessment of an advanced two-stage process is undertaken. • A comparison of the impacts of the process when fed with 7 feedstock is presented. • Sensitivity analysis on the system is performed. • The treatment of RDF shows the lowest impact in terms of both GWP and AP. • The plasma shows a small contribution to the overall impact of the plant. - Abstract: In the past, almost all residual municipal waste in the UK was landfilled without treatment. Recent European waste management directives have promoted the uptake of more sustainable treatment technologies, especially for biodegradable waste. Local authorities have started considering other options for dealing with residual waste. In this study, a life cycle assessment of a future 20 MWe plant using an advanced two-stage gasification and plasma technology is undertaken. This plant can thermally treat waste feedstocks with different composition and heating value to produce electricity, steam and a vitrified product. The objective of the study is to analyse the environmental impacts of the process when fed with seven different feedstocks (including municipal solid waste, solid refuse fuel, reuse-derived fuel, wood biomass and commercial & industrial waste) and identify the process steps which contribute more to the environmental burden. A scenario analysis on key processes, such as oxygen production technology, metal recovery and the appropriate choice for the secondary market aggregate material, is performed. The influence of accounting for the biogenic carbon content in the waste from the calculations of the global warming potential is also shown. Results show that the treatment of the refuse-derived fuel has the lowest impact in terms of both global warming potential and acidification potential because of its high heating value. For all the other impact categories analysed, the two-stage gasification and plasma process shows a negative impact for all the waste streams considered, mainly due to the avoided burdens associated with the production of electricity from the plant. The plasma convertor, key characteristic of the thermal process investigated, although utilising electricity shows a relatively small contribution to the overall environmental impact of the plant. The results do not significantly vary in the scenario analysis. Accounting for biogenic carbon enhanced the performance of biomass and refuse-derived fuel in terms of global warming potential. The main analysis of this study has been performed from a waste management perspective, using 1 ton of waste as functional unit. A comparison of the results when 1 kWhe of electricity produced is used as functional unit shows similar trends for the environmental impact categories considered.
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The uncertain supply of the rare-earth elements (REE) from conventional sources such as bastnaesite and monazite demands the search for alternative sources. Unconventional sources such as phosphate rock and mine tailings have REE contents at the level of only hundreds to a thousand parts per million, which challenges the conventional REE separation methods such as solvent extraction (SX) and ion exchange (IX). Alternatively, the potential of extraction chromatography (EXC) has been explored, as it combines the selectivity of SX and the convenience of column techniques of IX. Herein, we report a novel EXC material incorporating N , N '-dimethyl- N , N '-dioctyl-3-oxa-diglycolamide (DMDODGA) into a porous solid support because DMDODGA exhibits higher extraction efficiency for REE in SX than does conventional N , N , N ', N '-tetraoctyl-3-oxa-diglycolamide (TODGA) and as also compared with similarly made conventional TODGA-based EXC material. The extraction of mixed REE by DMDODGA and TODGA resins was evaluated in H 2 SO 4 , HCl, and HNO 3 media as a function of acid concentration. The REE feed concentrations were adjusted to achieve stoichiometric REE concentration and excess REE concentration, conditions that reflect near or complete saturation of resin capacity. In general, extraction at the same acid concentration followed the order HNO 3 > HCl > H 2 SO 4 . The extraction strength of the DMDODGA resin is significantly higher than that of the TODGA resin in all three examined mineral acids, especially at lower H 2 SO 4 and HCl concentrations (0.01 and 0.1 M), making it a promising EXC material for hydrometallurgical extraction of REE.
Using ambient pressure X-ray photoelectron spectroscopy (APXPS) and high pressure scanning tunneling microscopy (HPSTM), we show that in equilibrium with 0.01–0.2 Torr of methanol vapor, at room temperature, the Cu(100) surface is covered with methoxy species forming a c(2 × 2) overlayer structure. In contrast, no methoxy is formed if the surface is saturated with an ordered oxygen layer, even when the methanol pressure is 0.2 Torr. At oxygen coverages below saturation, methanol dissociates and reacts with the atomic oxygen, producing methoxy and formate on the surface, and formaldehyde that desorbs to the gas phase. Unlike the case of pure carbon monoxide and carbon dioxide, methanol does not induce the restructuring of the Cu(100) surface. These results provide insight into catalytic anhydrous production of aldehydes.
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Two dimensional (2D) materials have found various applications because of their unique physical properties. For example, graphene has been used as the electron transparent membrane for liquid cell transmission electron microscopy (TEM) due to its high mechanical strength and flexibility, single-atom thickness, chemical inertness, etc. Here, we report using 2D MoS 2 as a functional substrate as well as the membrane window for liquid cell TEM, which is enabled by our facile and polymer-free MoS 2 transfer process. This provides the opportunity to investigate the growth of Pt nanocrystals on MoS 2 substrates, which elucidates the formation mechanisms of such heterostructured 2D materials. We find that Pt nanocrystals formed in MoS 2 liquid cells have a strong tendency to align their crystal lattice with that of MoS 2 , suggesting a van der Waals epitaxial relationship. Importantly, we can study its impact on the kinetics of the nanocrystal formation. Here, the development of MoS 2 liquid cells will allow further study of various liquid phenomena on MoS 2 , and the polymer-free MoS 2 transfer process will be implemented in a wide range of applications.
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Elucidating the chemical kinetics of stabilized Criegee intermediates (sCIs) in the atmosphere is critically important for climate modeling. Here, we report a class of very rapid bimolecular reactions of two sCIs, namely, CH 2 OO and syn-CH 3 CHOO, with amides. We used electronic structure calculations and kinetics calculations to elucidate a universal mechanism by which the oxygen atom of the carbonyl group in an amide is added to the carbon atom of the COO group in the sCI with simultaneous transfer of the amide hydrogen to the terminal oxygen atom of the carbonyl oxide of the sCI. The barriers for the mechanism are submerged below reactants by ∼9 kcal/mol, which means that the tight transition state is not the rate-determining step, and the rate constants are determined by loose free energy bottlenecks between the reactants and the precursor complexes. We calculate the rate constants due to these loose and barrierless transition states by variable-reaction-coordinate variational transition-state theory. We find that bimolecular reactions of sCIs with amides are very rapid, with rate constants 1 to 5 × 10 –10 cm 3 molecule –1 s –1 , which is a factor of 2 faster than the rate constants of carboxylic acids with sCIs and 10 2 faster than the rate constants of OH reactions with amides. This has the consequence that, under a wide range of conditions, sCIs are the major sink for atmospheric amides, in contrast to the usual assumption that OH radicals are the dominant sinks.