Toward Financially Viable Phytoextraction and Production of Plant-Based Palladium Catalysts.

Although a promising technique, phytoextraction has yet to see significant commercialization. Major limitations include metal uptake rates and subsequent processing costs. However, it has been shown that liquid-culture-grown Arabidopsis can take up and store palladium as nanoparticles. The processed plant biomass has catalytic activity comparable to that of commercially available catalysts, creating a product of higher value than extracted bulk metal. We demonstrate that the minimum level of palladium in Arabidopsis dried tissues for catalytic activity comparable to commercially available 3% palladium-on-carbon catalysts was achieved from dried plant biomass containing between 12 and 18 g·kg-1 Pd. To advance this technology, species suitable for in-the-field application: mustard, miscanthus, and 16 willow species and cultivars, were tested. These species were able to grow, and take up, palladium from both synthetic and mine-sourced tailings. Although levels of palladium accumulation in field-suitable species are below that required for commercially available 3% palladium-on-carbon catalysts, this study both sets the target, and is a step toward, the development of field-suitable species that concentrate catalytically active levels of palladium. Life cycle assessment on the phytomining approaches described here indicates that the use of plants to accumulate palladium for industrial applications has the potential to decrease the overall environmental impacts associated with extracting palladium using present-day mining processes.

Intelligent Approach to Solvent Substitution: The Identification of a New Class of Levoglucosenone Derivatives.

With the increasing restriction and control of hazardous solvents, safer alternatives need to be identified. Here a contemporary approach to solvent selection and substitution is presented that offers a more scientific alternative to the simple "like-for-like" exchange. A new family of levoglucosenonederived compounds is proposed, modeled to determine their solvent properties, synthesized, and tested. These new molecules show promise as replacements for polar aprotic solvents that have chronic toxicity issues, such as dichloromethane, nitrobenzene, and N-methylpyrrolidinone. The success of this approach makes it possible for academia and industry to make calculated, intelligent choices for solvent substitution in the future.

Economic Assessment of Supercritical CO2 Extraction of Waxes as Part of a Maize Stover Biorefinery.

To date limited work has focused on assessing the economic viability of scCO2 extraction to obtain waxes as part of a biorefinery. This work estimates the economic costs for wax extraction from maize stover. The cost of manufacture (COM) for maize stover wax extraction was found to be € 88.89 per kg of wax, with the fixed capital investment (FCI) and utility costs (CUT) contributing significantly to the COM. However, this value is based solely on scCO2 extraction of waxes and does not take into account the downstream processing of the biomass following extraction. The cost of extracting wax from maize stover can be reduced by utilizing pelletized leaves and combusting the residual biomass to generate electricity. This would lead to an overall cost of € 10.87 per kg of wax (based on 27% combustion efficiency for electricity generation) and €4.56 per kg of wax (based on 43% combustion efficiency for electricity generation). A sensitivity analysis study showed that utility costs (cost of electricity) had the greatest effect on the COM.

Opportunities for Bio-Based Solvents Created as Petrochemical and Fuel Products Transition towards Renewable Resources.

The global bio-based chemical market is growing in size and importance. Bio-based solvents such as glycerol and 2-methyltetrahydrofuran are often discussed as important introductions to the conventional repertoire of solvents. However adoption of new innovations by industry is typically slow. Therefore it might be anticipated that neoteric solvent systems (e.g., ionic liquids) will remain niche, while renewable routes to historically established solvents will continue to grow in importance. This review discusses bio-based solvents from the perspective of their production, identifying suitable feedstocks, platform molecules, and relevant product streams for the sustainable manufacturing of conventional solvents.

Generation, capture, and utilization of industrial carbon dioxide.

As a carbon-based life form living in a predominantly carbon-based environment, it is not surprising that we have created a carbon-based consumer society. Our principle sources of energy are carbon-based (coal, oil, and gas) and many of our consumer goods are derived from organic (i.e., carbon-based) chemicals (including plastics, fabrics and materials, personal care and cleaning products, dyes, and coatings). Even our large-volume inorganic-chemicals-based industries, including fertilizers and construction materials, rely on the consumption of carbon, notably in the form of large amounts of energy. The environmental problems which we now face and of which we are becoming increasingly aware result from a human-induced disturbance in the natural carbon cycle of the Earth caused by transferring large quantities of terrestrial carbon (coal, oil, and gas) to the atmosphere, mostly in the form of carbon dioxide. Carbon is by no means the only element whose natural cycle we have disturbed: we are transferring significant quantities of elements including phosphorus, sulfur, copper, and platinum from natural sinks or ores built up over millions of years to unnatural fates in the form of what we refer to as waste or pollution. However, our complete dependence on the carbon cycle means that its disturbance deserves special attention, as is now manifest in indicators such as climate change and escalating public concern over global warming. As with all disturbances in materials balances, we can seek to alleviate the problem by (1) dematerialization: a reduction in consumption; (2) rematerialization: a change in what we consume; or (3) transmaterialization: changing our attitude towards resources and waste. The "low-carbon" mantra that is popularly cited by organizations ranging from nongovernmental organizations to multinational companies and from local authorities to national governments is based on a combination of (1) and (2) (reducing carbon consumption though greater efficiency and lower per capita consumption, and replacing fossil energy sources with sources such as wind, wave, and solar, respectively). "Low carbon" is of inherently less value to the chemical and plastics industries at least in terms of raw materials although a version of (2), the use of biomass, does apply, especially if we use carbon sources that are renewable on a human timescale. There is however, another renewable, natural source of carbon that is widely available and for which greater utilization would help restore material balance and the natural cycle for carbon in terms of resource and waste. CO(2), perhaps the most widely discussed and feared chemical in modern society, is as fundamental to our survival as water, and like water we need to better understand the human as well as natural production and consumption of CO(2) so that we can attempt to get these into a sustainable balance. Current utilization of this valuable resource by the chemical industry is only 90 megatonne per year, compared to the 26.3 gigatonne CO(2) generated annually by combustion of fossil fuels for energy generation, as such significant opportunities exist for increased utilization of CO(2) generated from industrial processes. It is also essential that renewable energy is used if CO(2) is to be utilized as a C1 building block.