Daniele Cespi

Life cycle inventory improvement in the pharmaceutical sector: assessment of the sustainability combining PMI and LCA tools

Pharmaceutical chemicals are complex, high value added products that typically impose significantly greater impacts on the environment per kilogram compared to basic chemicals. A variety of green metrics have been developed to guide the design of chemistries and processes that are more sustainable. Among these, Process Mass Intensity (PMI) was selected by the American Chemical Society Green Chemistry Institute Pharmaceutical Roundtable as the key parameter to express sustainability. However, researchers were concerned that these metrics could miss relevant factors that would be addressed by a more comprehensive Life Cycle Assessment (LCA). Lack of inventory data for many chemicals poses a significant barrier to more extensive implementation of LCA for pharmaceuticals. A cradle-to-gate LCA of Viagra™ is used to present a practical approach to construct inventories using patent and literature data. Details of the improved inventory data were presented for four chemicals to illustrate the methodology and highlight the importance of considering out-sourced processing of reagents used in pharmaceutical synthesis. A more comprehensive impact assessment was conducted using ReCiPe v1.11 at both midpoint and endpoint levels. A comparison of two synthesis routes rated them well against results from the simpler green metrics. An area for future work is to address the lack of characterization factors for toxicity and other impact categories for many chemicals.

Butadiene from biomass, a life cycle perspective to address sustainability in the chemical industry

In the past few decades, innovative approaches such as Green Chemistry and Green Engineering have come out in order to set the basic principles for a more sustainable chemical industry. However, researchers also need a more scientific and quantitative tool to address the sustainability behind the application of those principles. Therefore, a multi-criteria approach based on life cycle thinking was proposed to investigate the production of 1,3-butadiene. Five indicators were selected to address sustainability: the Cumulative Energy Demand, the carbon footprint, the water depletion, a midpoint-oriented analysis method and an economic index. The use of renewable feedstock was evaluated in comparison with the traditional fossil-based route from naphtha. Two alternative pathways which use bio-ethanol were considered – the Lebedev and Ostromisslensky processes – evaluating the possibility to locate the plant in three different regions (the EU, Brazil and the US). Detailed analysis reveals how the use of bio-based feedstock leads to a significantly lower consumption of fossil sources, despite the higher exploitation of renewable resources leading to larger water withdrawals. Moreover, the assessment of the global warming potential reveals how bio-routes are far from able to be considered carbon-neutral. In addition, the ReCiPe single-score was used, showing greater sustainability of the Lebedev process compared with the traditional way. On the other hand, the two-step pathways (Ostromisslensky) result in the worst scores. An economic evaluation was also applied. The index reveals how the direct conversion into 1,3-butadiene seems more suitable than the two-step method, particularly in the case of production in the US.

Glycerol as feedstock in the synthesis of chemicals: a life cycle analysis for acrolein production

Glycerol is an important bio-platform molecule, potentially usable for the synthesis of various chemicals and fuel additives, the synthesis of acrolein by dehydration being one of the most studied reactions. Through the application of the life cycle assessment (LCA) methodology we investigated the production of acrolein from glycerol, by comparing two alternative scenarios in which glycerol is obtained as a co-product either in triglyceride trans-esterification to FAME or in hydrolysis to fatty acids. Our results show how the main impacts are not related to the energy involved in the two processes. In fact, the use of dedicated crops as a source of triglycerides in the biodiesel production entailed higher impacts in terms of land exploitation. On the other hand, beef tallow was assumed as a starting raw material in the production of fatty acids, and this involved some significant impacts associated with animal rearing. At the same time, however, avoiding the use of dedicated biomass ensured a lower global impact (in terms of single scores). Lastly, in order to validate the model created, a sensitivity analysis using the Monte Carlo method was performed. The two routes from glycerol were also compared with the classical chemical route where acrolein is produced by propylene oxidation.

A simplified early stage assessment of process intensification: glycidol as a value-added product from epichlorohydrin industry wastes

The present work deals with the production of glycidol through a new synthetic approach based on the conversion of 2-chloro-1,3-propanediol (β-MCH), a by-product in the epichlorohydrin production plant. β-MCH was converted with high yield (90%) and selectivity (99%) to glycidol using an alcoholic solution of KOH at room temperature in only 30 minutes. A simplified early stage assessment based on the use of the green metrics and a life cycle analysis were adopted in order to evaluate the environmental feasibility of this innovative route if compared with the traditional chain to epichlorohydrin. The waste recovery and the maximization of the overall process efficiency lead to sensible reductions per each indicator considered in the assessment, suggesting the possibility of developing on a full industrial scale. In addition, in order to verify the potentialities behind the substitution of the fossil-based glycidol with the product resulted from the recovery of the β-MCH, a cradle-to-gate analysis and the GREENMOTION® tool were adopted.

Glycidol, a Valuable Substrate for the Synthesis of Monoalkyl Glyceryl Ethers: A Simplified Life Cycle Approach

The disposal of any waste by recovering it within the production plant represents the ultimate goal of every biorefinery. In this scenario, the selective preparation of monoalkyl glyceryl ethers (MAGEs) starting from glycidol, obtained as byproduct in the epichlorohydrin production plant, represents a very promising strategy. Here, we report the synthesis of MAGEs through the reaction of glycidol with alcohols catalyzed by a green homogeneous Lewis acids catalyst, such as BiIII triflate, under very mild reaction conditions. To evaluate the green potential of the proposed alternative, a simplified life cycle assessment (LCA) approach was followed by comparing the environmental performance of the proposed innovative route to prepare MAGEs with that of the most investigated pathway from glycerol. A considerable reduction of all impact categories considered was observed in our experimental conditions, suggesting that the glycidol-to-MAGEs route can be a valuable integration to the glycerol-to-MAGEs chain. Thanks to the use of primary data within the LCA model, the results achieved are a very good approximation of the real case.

Application of switchable hydrophilicity solvents for recycling multilayer packaging materials

A new procedure based on switchable hydrophilicity solvents (SHS) was proposed for polyethylene and aluminium recovery from food aseptic packaging. Treatment with N,N-dimethylcyclohexylamine (DMCHA) allowed very high material recovery (>99% for aluminium and >80% for polyethylene), without compromising the quality in terms of oxidation or polymer degradation. Moreover, the results from a simplified and preliminary life cycle analysis confirm the potential environmental benefits of a SHS approach compared with other treatment and disposal scenarios.

First Attempt of Glycidol-to-Monoalkyl Glyceryl Ethers Conversion by Acid Heterogeneous Catalysis: Synthesis and Simplified Sustainability Assessment

The selective preparation of monoalkylglyceryl ethers (MAGEs) is a task for researchers owing to their broad range of applications. In this work, green feedstocks such as glycidol and alcohols were used to prepare MAGEs under mild reaction conditions (80 °C, 3 h, 0.5 mol % catalyst) in the presence of acid heterogeneous catalysts. Nafion shows the best performances in terms of conversion and selectivity to MAGES and also high stability. A comparison of the environmental performances with the most consolidated pathway from glycerol has shown that the usage of glycidol (recovered as a value-added product from Epicerol process) and Nafion leads to a lower impact on ecosystems. In addition, results achieved from a simplified socio-economic analysis show that the innovative route here proposed has potential (at the laboratory scale) of enhancing potential gains and of reducing the social implications resulting from externalities associated with environmental impacts (e.g., CO2 equivalents).

The Frontier of Biobased Polymers: Synthesis, Characterization, Application, and Sustainability Assessment

1Tyndall National Institute, University College Cork, Dyke Parade, Cork, Ireland 2Environmental Management and Consulting (EMC) Innovation Lab S.r.l., Viale Italia 29, 47921 Rimini, Italy 3Apollo Tyres Ltd., Chennai, India 4School of Engineering and Applied Science, The George Washington University, Washington, DC 20052, USA 5Dipartimento di Chimica e Biologia “Adolfo Zambelli”, Università di Salerno, Via Giovanni Paolo II, 132-84084 Fisciano, Italy