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Issue 02/2018

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Report Polyamides from

Report Polyamides from fish waste and more We move forward by leaps and bounds. To meet the needs of a society in constant flux, human beings are consuming our planet’s resources in increasingly larger quantities – a process that is exacerbated by the exponential growth of the number of inhabitants and the recent development of traditionally poor areas. DAFIA is a project developed with EU funds and focused on the valorisation of municipal solid waste and marine rest raw materials (MRRM). The project was established with the aim of reducing the environmental impact of these materials and of giving them a second life. Fifteen companies and research centres are taking part in this project, which is being led by the Spanish Plastics Technology Centre AIMPLAS. The other participants (Politecnico di Torino, Sintef Ocean, Sintef Materials and Chemistry, DTU, Ircelyon, Nutrimar, IRIS, Biotrend, Daren Labs, Mine Colours, Bio Base Europe, Biopolis, Arkema and National Non-Food Crops Centre) hail from a range of countries, including Spain, Italy, Norway, Denmark, France, Portugal, Israel, Turkey, Belgium and United Kingdom. Currently, 50 % of all waste in the EU is still landfilled, despite the fact that this practice is associated with environmental contamination and a consequent reduction in the life quality of millions of Europeans. Similarly, more than 1.3 million tonnes of residual raw materials from the fishing industry are generated in the EU each year. Rather than disposing of this waste, a better idea is to reuse it: by transforming it into high added-value products able to provide sustainable resources to society. These products, developed within the DAFIA project, will be selected based on their value and commercial viability. Furthermore, their exploitation will create synergies between the different industries along the value-chain. DAFIA is a great challenge. One of the main aims is the development and commercialization of conversion routes to produce chemical building blocks, i.e. molecules with reactive functional groups that can be transformed into new products for the market; products such as dicarboxylic acids and diamines, which can be polymerized to obtain polyamides. The biogenic fraction of municipal solid waste (MSW) - the biobased fraction of park and garden waste and the waste collected from households, restaurants, caterings and commercial premises - constitutes between 30 and 50 % of the total MSW. Currently, only 30 % of this amount is recycled; 50 % is landfilled and the remaining 20 % is incinerated. DAFIA’s challenge is to develop conversion solutions that yield higher added-value products than achieved with current methods. On the other hand, thousands of tonnes of fish are discarded into European waters due to a lack of suitable infrastructure and processing technologies, a practice that, until recently, was allowed by European marine policies. Traditionally, some countries have used MRRM as silage, turning it into feed for animals or fish, or as raw material for anaerobic digesters. Only a small part of these residual materials is currently used for human consumption or in high added-value applications. Although recent reforms in the common fisheries policy (CFP) seek to introduce changes in these practices, the development of new methods to turn these fractions into profitable products is still a challenge for the industry. DAFIA aims to accelerate this process. A life cycle and techno-economic viability assessment will be conducted to evaluate the project’s objectives. DAFIA’s main line: to take advantage of this waste The technological developments for treating the organic fraction of MSW have focused mainly on improving degradability and conversion into biogas and compost as the main solution for non-recycled bioresidues. This includes chemical, physical and biological pre-treatments to improve the bioavailability and separation of the target compounds, thus reducing unwanted processes, such as uncontrolled fermentation due to contamination by microorganisms, or their degradation. DAFIA will explore two ways for using MSW: as a whole, or by using isolated components as substrates for fermentation for production of diamines or diacids. For both approaches, pre-treatment processes are being developed, combining biotechnological and physical-chemical processes, while keeping in mind the natural variability of the resources. Other extracts from by-products of the fishing industry are nucleic acids (including DNA and RNA) and gelatine, which derive from viscera, skin and fish bones respectively. The amount of nucleic acids in the waste varies, depending on the organs. The strategies for their extraction and purification are not extensively described in the scientific literature and many define the extraction of a particular tissue by means of laboratory-scale kits. For its correct purification, four important steps are required: the disruption of gels or tissues, the denaturation of protein complexes, the inactivation of nucleases and the elimination of lipids or carbohydrates and contaminant proteins. DAFIA is working to develop procedures to be able to carry out these steps, targeting nucleic acids from fish viscera. The extraction methods for the different raw materials are being optimized (fish residues and co-fractions after other technological processes), as are the different extraction parameters (temperature, time, pH, fractionation of extracts, etc.). A subsequent separation step is applied to improve the properties and yield of the nucleic acids and gelatine obtained. 48 bioplastics MAGAZINE [02/18] Vol. 13

Report By: José María García Pérez, Synthesis department AIMPLAS Paterna (Valencia) Spain The major challenge: providing added value to products currently without utility The researchers in the DAFIA project have chosen to use yeasts to produce diacids, as these are highly suitable for fermentations at industrial scale with the GRAS status (generally recognized as safe). Conducting fermentation at low pH values has two advantages: there is less risk of contamination by bacteria, and it allows for the production of organic acids in their undissociated form, thus reducing the purification costs. DAFIA seeks to develop fermentation processes to produce diacids at a minimum level of 5g/kg, and at least at 5g/kg of diamines from MSW, carbohydrates, fats and proteins. A minimum of 70 % of the protein and lipid fractions in MSW will be converted. Moreover, DAFIA seeks to develop a new range of flame retardants based on nucleic acids by means of more environmentally friendly chemical routes (free of organic solvents). They will be used as thermoplastic fire protectors, as a viable alternative to ammonium polyphosphate. As a thermal requirement, an insignificant loss of the host polymer’s mechanical behaviour is expected. Another substance obtained from marine residues is gelatine. Gelatine is modified and purified collagen, and it is the main protein component of skin, cartilage and bone tissues. Due to its unique properties, it is widely used in the food, pharmaceutical and cosmetics sectors and in photographic applications. It is mainly derived from pigs and sheep, but fish gelatine is offers an excellent alternative to gelatine derived from mammal sources. Furthermore, various amino acids and diamines are used as the monomers in the synthesis of polyamides and other polymers. DAFIA will investigate the use of these renewablysourced acids as additives for diverse applications in polyamides and as a source for diamine synthesis, thanks to the development of new routes. DAFIA’s objective is mainly the synthesis of different polyamides, with a bio-content of close to 100 %. For that purpose, di-acids and diamines from fermentation of MSW will be used to obtain building blocks and intermediates. Outlook At the end of this European project, the participants of DAFIA hope to obtain three high-value bio-chains: flame retardants from nucleic acids; gelatine coatings for food packaging applications; and chemical building blocks, such as dicarboxylic acids and diamines from carbohydrate, lipid and protein fermentation processes. The project is also assessing alternatives to high-volume oil-based chemical products, such as flame retardants, coatings and polyamides. New markets and applications are being explored, based on their improved functionalities. Urban Waste Fish Industry By-Product Multifedstock Biorefinery Polyamides Fish Industry By-Product Energy & Others BioChemicals Flame retardants Green Chemistry Biopackaging bioplastics MAGAZINE [02/18] Vol. 13 49

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