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ACS Sustainable Chemistry & Engineering Perspective sustainability of commodity chemicals from renewable biomass. In the first place, it will be necessary to measure and compare the suitability of different waste lignocellulosic feedstocks. Girio and co-workers111 proposed a Biotechnological Valorization Potential Indicator (BVPI), based on biological, physicochem- ical, technological, economic, and geographical factors, for measuring the suitability of lignocellulosic materials as feedstocks for a biorefinery. Using their BVPI, they were able to identify several lignocellulosic waste streams from the Portuguese agro-industrial sector, for example, rice husks and tomato pomace, with high valorization potential. Saling and co-workers112,113 at BASF used eco-efficiency analysis for a cradle-to-gate assessment of biobased vs petroleum-based routes to, for example, vitamin B2 (riboflavin). However, there is a great need for concise methodologies for assessing the sustainability of biobased vs petrochemical-based routes to commodity chemicals. Patel and co-workers,114 building on earlier work of Sugiyama and co-workers,115 described a methodology for relatively quick, preliminary assessment of the sustainability of processes in the laboratory phase based on a multicriteria approach comprising green chemistry principles, techno-economic analysis, and some elements of LCA, reflecting the environmental impact of both the raw materials and the process. Five parameters contributed to the final score: 1. Economic constraints (weighting 0.3) • Raw materials costs/value of product and coproducts 2. Environmental impact of the raw materials (weighting 0.2) • Cumulative energy demand • GHG emissions 3. Costs and environmental impact of the process (weighting 0.2) • Mass loss index = total mass of all materials/ mass of product + coproducts) 4. Environment, Health, and Safety (EHS) index (weight- ing 0.2) • Hazards and persistency of emissions (environ- ment) • Chronic toxicity and irritation (health) • Acute toxicity and fire/explosion hazards (safety) 5. Risk assessment (weighting 0.1) • For example, feedstock availability and supply The method was used to compare biobased vs naphtha-based butadiene and was later extended to other early stage biobased vs petroleum-based products.116,117 A more comprehensive study of biobased vs naphtha-based butadiene, using a simplified life cycle approach based on five indicators cumulative energy demand, carbon footprint, water usage, and an economic indexwas subsequently reported by Cavani and co-workers.118 They concluded that the direct conversion of (bio)ethanol to butadiene has a lower burden than the naphtha-based route and that future efforts should be focused on this route. The European Union COST Action CM0903 “Utilization of Biomass for Sustainable Fuels and Chemicals” (UBIOCHEM) was launched in November 2009 with special emphasis on the utilization of agricultural residues and nonedible or waste triglycerides. An important objective of UBIOCHEM was to shape a unified view and develop concise metrics for comparing L different processes to sustainable fuels and platform chemicals from biomass. A special issue of Catalysis Today, “Sustainability Metrics of Chemicals from Biomass”, was devoted to this topic in 2015.119 The goal was to produce a concise set of sustainability metrics which would enable a relatively quick, cradle-to-gate comparison of fossil-based vs renewable biomass-based routes to commodity chemicals. It soon became apparent that mass- based metrics alone were not sufficient to differentiate as the competing processes often had comparable E factors. Four criteria were eventually selected: material and energy efficiency, land use, and process economics.120 1. Material efficiency • Mass of useful products/total mass of useful products + waste, that is, it is 1/E + 1 2. Energy efficiency • Caloric value of useful products/caloric value of fossil and renewable energy inputs 3. Land use • Hectares of land (in Champagne, France) of good agricultural soil per tonne product 4. Process economics • Raw material and capital costs • Starting point for petrochemical route • Starting point for biobased route is sugar beet, corn, or rapeseed. Seven commodity chemicals were chosen for the study: lactic acid,121 acrylonitrile,122 1-butanol,123 1,2-propane diol,124 succinic acid,125 isoprene,126 and methionine.127 An overall conclusion was that some chemicals (for example, lactic acid) can already be produced from biomass with less energy input and even at lower cost compared to established petrochemical routes, while others are currently more expensive and less energy efficient. Indeed, many biobased routes are at the beginning of the learning curve, and these concise metrics are useful in identifying bottlenecks and providing a basis for planning further research on optimization. When the relevant processes have been demonstrated at an industrial scale, full-blown sustainability assessments can be used to compare different process strategies. For example, Morales and co-workers128 carried out a sustainability assess- ment of technologies for the production of succinic acid by fermentation with metabolically engineered strains of E.coli, including isolation of the succinic acid from the fermentation broth. Technical, economic, environmental, and process hazard aspects were considered. They showed that fermentation with strains active at acidic pH together with reactive extraction of the product provide the most environmentally competitive process, while strains with resistance to high sugar concen- trations afforded the most economically attractive one. Succinic acid is currently produced mainly from n-butane via maleic anhydride. Substitution of this petrochemical succinic acid by biosuccinic acid would afford greenhouse gas savings of ca. 5 tonnes of CO2 per tonne of succinic acid. The authors noted that realization of a high market share is dependent on a future decrease in total production costs, and the product isolation step is responsible for 60−70% of the latter. Interestingly, Horvath and co-workers129 proposed “ethanol equivalent”, a novel and relatively simple metric, as a common currency for assessing the sustainability of biomass-based routes to fuels and chemicals. An ethanol equivalent is defined as the mass of ethanol required to deliver the equivalent amount of energy from a given feedstock using energy equivalency or DOI: 10.1021/acssuschemeng.7b03505 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXXPDF Image | Metrics of Green Chemistry and Sustainability
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