Fire Propagation Behavior of Some Biobased Furanic Compounds with a Focus on the Polymer PEF.

Avantium is in the process of building a flagship plant for the production of furandicarboxylic acid (FDCA) and the derived polyester polyethylene furanoate (PEF) using their YXY process. Because of the status of this development of monomer production, next to storage and shipping, polymer production, application development, and polymer recycling, the understanding of the safety aspects of the YXY process is key for a successful deployment of the technology. In this paper, the focus is on fire propagation-related issues for both monomeric furanic compounds and for the polymer PEF and results are compared with relevant reference materials. The current assessment addresses the fire initiation and propagation behavior of FDCA and PEF for the very first time. From the fire safety viewpoint, it can be concluded that of the furanics tested, FDCA has a better safety margin both in terms of a lower thermal and chemical threat, as fires resulting from FDCA are not easily shifting toward underventilated fire scenarios. The obtained results with the PEF polymer are useful in understanding the nature and behavior of PEF under real fire conditions. PEF seems slightly better in terms of the total energy released from the combustion process than the bulk polyester PET. In addition, PEF fires result in lesser CO and soot yields compared to PET, which is proof for a better completeness of combustion.

Enhancing the Antioxidant Activity of Technical Lignins by Combining Solvent Fractionation and Ionic-Liquid Treatment.

A grass soda technical lignin (PB1000) underwent a process combining solvent fractionation and treatment with an ionic liquid (IL), and a comprehensive investigation of the structural modifications was performed by using high-performance size-exclusion chromatography, 31 P NMR spectroscopy, thioacidolysis, and GC-MS. Three fractions with distinct reactivity were recovered from successive ethyl acetate (EA), butanone, and methanol extractions. In parallel, a fraction deprived of EA extractives was obtained. The samples were treated with methyl imidazolium bromide ([HMIM]Br) by using either conventional heating or microwave irradiation. The treatment allowed us to solubilize 28 % of the EA-insoluble fraction and yielded additional free phenols in all the fractions, as a consequence of depolymerization and demethylation. The gain of the combined process in terms of antioxidant properties was demonstrated through 2,2-diphenyl-1-picrylhydrazyl (DPPH. ) radical-scavenging tests. Integrating further IL safety-related data and environmental considerations, this study paves the way for the sustainable production of phenolic oligomers competing with commercial antioxidants.

Hydrolysis of Hemicellulose and Derivatives-A Review of Recent Advances in the Production of Furfural.

Biobased production of furfural has been known for decades. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve production modes and expand potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of furfural production from sugars and polysaccharides feedstocks. The review discusses advances obtained in major production pathways recently explored splitting in the following categories: (i) non-catalytic routes like use of critical solvents or hot water pretreatment, (ii) use of various homogeneous catalysts like mineral or organic acids, metal salts or ionic liquids, (iii) feedstock dehydration making use of various solid acid catalysts; (iv) feedstock dehydration making use of supported catalysts, (v) other heterogeneous catalytic routes. The paper also briefly overviews current understanding of furfural chemical synthesis and its underpinning mechanism as well as safety issues pertaining to the substance. Eventually, some remaining research topics are put in perspective for further optimization of biobased furfural production.

Comprehensive Insights into the Thermal Stability, Biodegradability, and Combustion Chemistry of Pyrrolidinium-Based Ionic Liquids.

The use of ionic liquids (ILs) as advanced electrolyte components in electrochemical energy-storage devices is one of the most appealing and emerging options. However, although ILs are hailed as safer and eco-friendly electrolytes, to overcome the limitations imposed by the highly volatile/combustible carbonate-based electrolytes, full-scale and precise appraisal of their overall safety levels under abuse conditions still needs to be fully addressed. With the aim of providing this level of information on the thermal and chemical stabilities, as well as actual fire hazards, herein, a detailed investigation of the short- and long-term thermal stabilities, biodegradability, and combustion behavior of various pyrrolidinium-based ILs, with different alkyl chain lengths, counteranions, and cations, as well as the effect of doping with lithium salts, is described.

Coupling of OECD standardized test and immunomarkers to select the most environmentally benign ionic liquids option--towards an innovative "safety by design" approach.

This paper proposed a potential industrial accompaniment to reduce ionic liquid harmfulness by a novel combination of OECD Daphnia magna standardized test and fish immunomarkers. The combination of these two tests allowed multicriteria examination of ILs impacts in different organisms and trophic levels. The work provided new data for legislation and opened a door towards an integrative environmental evaluation due to direct implications of immune system in fish and ecosystem health. Whatever the species, each IL tested induced deleterious effects suggesting that toxic impact was especially due to IL lipophilicity properties. Nevertheless, cation moieties of ILs seemed to draw overall toxicity of ILs to significant extent as supported by lower cell mortality shown with imidazolium-based ILs compared to phosphonium-based ILs. However, the anions moieties have some additional effect, as revealed by quite dissimilar toxicity within same IL family. Concerning the more integrative biomarkers, the cationic-based ILs tested possessed also dissimilar effect on immune system of fish, especially on leucocyte distribution, lysosomal membrane integrity and phagocytosis activity. These results confirm that ILs toxicity could be influenced by design and that chemical engineering processes can integrate ecological footprint reduction strategies for successful IL utilization in the future.

In-depth safety-focused analysis of solvents used in electrolytes for large scale lithium ion batteries.

To better rule out the complex fire risk related to large format lithium ion cells, a detailed and systematic evaluation, both at component and cell levels, could be an invaluable milestone. Therefore, combustion analysis was conducted for major single organic solvents and their mixtures used in lithium ion battery technology, both in oxygen rich and lean environments using a Tewarson calorimeter. Well controlled test conditions have enabled the determination of key parameters governing the fire induced hazards such as flash point, ease of ignition, heat release rate, effective heat of combustion, specific mass loss rate, as well as the assessment of fire induced toxicity. Moreover, a rule of thumb for the screening of new solvents including the safety perspective such as the Boie correlation and N-factor were introduced for predicting the heat of combustion and combustion kinetics, respectively, prior to conducting any experimental work. Fire induced toxicity of single solvents and their mixtures was also briefly examined by performing toxic gas measurements.

Safety and security issues relating to low capacity storage of AN-based fertilizers.

Motivated by both the Toulouse explosion, and a series of recent unexpected handling and storage accidents in well-developed countries, the safety issues associated with the storage of fertilizer grades of ammonium nitrate (AN) are considered with a focus on low storage capacity premises. Such facilities are numerous and, in large agricultural countries, include thousands of end-users and hundreds of small distributors. The strong oxidative (sometimes explosive) properties of products containing significant amounts of AN have led to a long history of major accidents including mass explosions in large storage units and pre 1950s, to mass explosions in ships. A major breakthrough in safety was achieved in the 1950s, with the promotion - amongst other improvements - of better anti-caking agents. Although modern AN fertilizers complying with current standards are not considered as explosive material per se, the latent risk of accidental detonation under specific conditions remains a real issue, and from a scientific point of view, cannot be completely ruled out-as dramatically demonstrated by the Toulouse disaster in France. The new insight provided here is derived from: (1) a literature review on hazardous properties of AN and AN-based fertilizers; (2) a review of accidents focusing more particularly on the reporting of recent new cases involving relatively small quantities of previously 'thought safe' products; (3) an examination of both the relevant regulatory framework and the level of hazard control achieved; (4) appropriate discussions of the economical, technical and organizational factors that could lead to some underestimation of the risk compared to large scale storage facilities. In terms of research requirements, the complex potential scenario 'mass explosion following a fire' requires further attention, as does the role and properties of molten ammonium nitrate, which could be the precursor for such an event to occur. Beyond research needs, reinforced legislative control by the authorities and further promotion of safe storage practices must be encouraged by the industry for end-users particularly. Such users have inherently the highest potential for undesirable situations, due both to the nature of their activities and also a possible lack of awareness of the real danger.