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 c...
A new concept is demonstrated for an integrated close to zero waste wheat straw biorefinery combining two novel green technologies, CO 2 extraction and low temperature microwave pyrolysis, to produce a variety of products, including energy and CO 2 which can be internally recycled to sustain the processes. CO 2 adds value to the process by extracting secondary metabolites including fatty acids, wax esters and fatty alcohols. Low temperature microwave pyrolysis (<200 C) is shown to use less energy and produce higher quality oils and chars than conventional pyrolysis. The oils can be fractionated to produce either transport fuels or platform chemicals such as levoglucosan and levoglucosenone. The chars are appropriate for co-firing. The quality of the chars was improved by washing to remove the majority of the potassium and chlorine present, lowering their fouling potential. The economic feasibility of a wheat straw biorefinery is enhanced by intergrating these technologies.
Supercritical carbon dioxide (scCO 2 ) can be used as a ''green'' selective solvent for extractions of wheat straw waxes. For the first time, the crude extraction yields of wheat straw waxes and the yields of a single high value group of components (wax esters) using various scCO 2 conditions (305.15 to 373.15 K and 7.5 to 40 MPa) have been modelled using the Chrastil equation (Chrastil, 1982). The model accurately predicts both the crude yield and percentage of valuable wax esters within the extracts enabling maximum extraction efficiency. The key compounds within the waxes (fatty acids, sterols, fatty alcohols, wax esters, b-diketones and alkanes) have been identified and quantified. This study highlighted that, 14,16 hentriacontanedione was extracted at critical temperature and pressure in concentrations of 1000 mg.g À1 straw. This molecule could demonstrate significant potential as a natural chelate for metal recovery and also in the formation of super-hydrophobic coatings.
Straw is a good example of a low-value, high-volume agricultural by-product that can be the basis for a biorefi nery, which should aim (to be truly sustainable and economically viable) to process the feedstock into a variety of valuable products cleanly and effi ciently. This article discusses a clean technology -supercritical carbon dioxide extraction, which can represent an ideal initial processing stage in a biorefi nery supplied with wheat straw or any appropriate biofeedstock. It also describes different biorefi ning scenarios and determines the potential economic benefi ts that might result from a coordinated structure. This working example is the culmination of four years of research undertaken by a consortium led by the University of York and consisting of a number of industrial and academic partners across the supply chain.
The biocatalytic generation of high-value chemicals from abundant, cheap and renewable feedstocks is an area of great contemporary interest. A strain of Rhodococcus erythropolis designated MLT1 was isolated by selective enrichment from the soil surrounding hop plants, using the abundant triene beta-myrcene from hops as a sole carbon source for growth. Resting cells of the organism were challenged with beta-myrcene, and the major product of biotransformation was determined by mass spectrometric analysis to be the monoterpene alcohol geraniol. Controls demonstrated that the product was biogenic and that an aerobic environment was required. The ability to transform beta-myrcene was shown to be restricted to cells that had been grown on this substrate as sole carbon source. Pre-incubation of cells with the cytochrome P450 inhibitors metyrapone or 1-aminobenzotriazole reduced geraniol production by 23% and 73% respectively, but reduction in activity was found not to correlate with the inhibitor concentration. A comparative analysis of insoluble and soluble cell extracts derived from cells of MLT1 grown on either beta-myrcene or glucose revealed at least four proteins that were clearly overproduced in response to growth on beta-myrcene. Mass spectrometric analysis of tryptic digests of three of these protein bands suggested their identities as an aldehyde dehydrogenase, an acyl-CoA dehydrogenase and a chaperone-like protein, each of which has a precedented role in hydrocarbon metabolism clusters in Rhodococcus sp. and which may therefore participate in a beta-myrcene degradation pathway in this organism.
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