A roadmap to a green chemical industry in Australia

Ananda, J ORCiD: 0000-0002-4072-6725A ‘roadmap’ has been devised for a progressive greening of the Australian chemical industry over the next two decades. The roadmap is based on a set of interactive principles broadly termed ‘economic’, ‘social’, ‘technological’, ‘environmental’ and ‘political’, which collectively form the ‘drivers of change’ in chemical industry strategy/business/policy planning—leading to greater efficiency and economic sustainability of this industry. The proposed roadmap pre-supposes that real economic, societal and environmental benefits can be obtained through greater use of existing and emerging green chemical technology. It can play an important role in developing a sustainable chemical industry in Australia. Primarily, the proposed roadmap involves a paradigm shift of the business operating plan and a significant mindset change of management

A roadmap to a green chemical industry in Australia

A ‘roadmap’ has been devised for a progressive greening of the Australian chemical industry over the next two decades. The roadmap is based on a set of interactive principles broadly termed ‘economic’, ‘social’, ‘technological’, ‘environmental’ and ‘political’, which collectively form the ‘drivers of change’ in chemical industry strategy/business/policy planning—leading to greater efficiency and economic sustainability of this industry. The proposed roadmap pre-supposes that real economic, societal and environmental benefits can be obtained through greater use of existing and emerging green chemical technology. It can play an important role in developing a sustainable chemical industry in Australia. Primarily, the proposed roadmap involves a paradigm shift of the business operating plan and a significant mindset change of management

High-Level Computer Molecular Modeling for Low-Rank Coal Containing Metal Complexes and Iron-Catalyzed Steam Gasification

Low-rank coal is a complex mixture; consequently, it is necessary to develop simpler molecular representations for computational modeling. Our modeling objective has been to develop molecules suitable for semi-empirical (SE) computations of low-rank coal containing transition-metal complexes. These molecular models contain oxygen functional groups that are macro-ligands, forming coordination complexes with specific three-dimentional (3D) orientations; consequently, we develop models that encapsulate the properties of low-rank coals and can form metal complexes. The large computer resources required for SE calculations of these molecules limited their size; of the models examined, those containing numerous short links between phenyl groups caused excessive strain and were unsuitable to model transition-metal complexes. Computations (SE) of our models provided data on (i) hydrogen bonds of coal containing water, (ii) formation of aqua−inorganic species and transition-metal complexes, (iii) pyrolysis chemistry involving transformations of metal hydroxide/oxides, (iv) routes for H₂ and CO formation, and (v) mechanism of iron-catalyzed steam gasification. Our char models, on the basis of transformations of the coal model, were consistent with low-temperature pyrolysis; these were disordered structures with some phenyl groups spaced between 0.35 and 0.4 nm. Smaller models of char and chars containing transition-metal clusters were optimized with SE and density functional theory (DFT) computations; these models were useful in modeling the mechanism of catalytic steam gasification. Our modeling of the mechanisms of iron-catalyzed steam gasification was consistent with experimental data

Density functional theory molecular modelling and experimental particle kinetics for CO2-char gasification

Experimental measurements and DFT atomistic modelling were conducted to elucidate the mechanisms for gasification chemistry of char with CO2 gas. The molecular models used were based on experimental representations of coal chars derived from the vitrinite- and inertinite-rich South African coals at 1000 °C. The HRTEM and XRD techniques were used to construct parallelogram-shaped PAH stacks of highest frequency in the vitrinite-rich (7 × 7) and intertinite-rich (11 × 11) char structures. Computations were executed to get the nucleophilic Fukui functions, at DFT–DNP level, to elucidate the nature and proportions of carbon active sites and quantify their reactivity. The DFT–DNP-computed reaction pathways and transition states, to obtain the energy of reaction and activation energies for the gasification reactions of CO2 with active carbon sites were examined. These results were compared with TGA experimental results at 900–980 °C. The mean nucleophilic Fukui function of the H-terminated char models and active sites located at similar edge positions decreased with increasing size of char molecules and followed the sequence: zigzag > armchair > tip active sites. The mean DFT–DNP values for the activation energy of 233 kJ mol−1 at the reactive carbon edge was in agreement with the experimental 191 ± 25 kJ mol−1 and 210 ± 8 kJ mol−1 for the respective chars