RESUMO
The conventional thermal method of preparing hafnium alkoxides [Hf(OR)4 , R=alkyl] - excellent precursors for gate-dielectric HfO2 on semiconductors - is severely hindered by its unsatisfactory environmental and economic burdens. Herein, we propose a promising electrodissolution-coupled Hf(OR)4 synthesis (EHS) system for green and efficient electrosynthesis of Hf(OR)4 . The operational principle of the electrically driven system consists of two simultaneous heterogeneous reactions of Hf dissolution and alcohol dehydrogenation, plus a spontaneous solution-based combination reaction. In applying ethanol as solvent and Hf metal as electrodissolution medium, we achieved waste-free production of high-purity hafnium ethoxide [Hf(OEt)4 ] with an equivalent "a concomitant" reduction in CO2 emission of 187.33â g CO2 per kg Hf(OEt)4 and a high net profit of 30 477â USD per kg Hf(OEt)4 . This system is very competitive with the thermal process, which unavoidably releases substantial waste and CO2 for a net profit of 27 700â USD per kg Hf(OEt)4 . We anticipate that the environmental and economic benefits of the EHS process could pave the way for its practical application.
Assuntos
Dióxido de Carbono , Háfnio , Metais , Semicondutores , SolventesRESUMO
Using a rigorous, rate-based model and a validated economic model, we investigated the technoeconomic performance of an aqueous NH3-based CO2 capture process integrated with a 650-MW coal-fired power station. First, the baseline NH3 process was explored with the process design of simultaneous capture of CO2 and SO2 to replace the conventional FGD unit. This reduced capital investment of the power station by US$425/kW (a 13.1% reduction). Integration of this NH3 baseline process with the power station takes the CO2-avoided cost advantage over the MEA process (US$67.3/tonne vs US$86.4/tonne). We then investigated process modifications of a two-stage absorption, rich-split configuration and interheating stripping to further advance the NH3 process. The modified process reduced energy consumption by 31.7 MW/h (20.2% reduction) and capital costs by US$55.4 million (6.7% reduction). As a result, the CO2-avoided cost fell to $53.2/tonne: a savings of $14.1 and $21.9/tonne CO2 compared with the NH3 baseline and advanced MEA process, respectively. The analysis of energy breakdown and cost distribution indicates that the technoeconomic performance of the NH3 process still has great potential to be improved.