Graphene Plus: reusable eco-innovative sorbent for oil spills clean-up and polluted water treatment Annalisa Pola, Giulio Cesareo, Gianni Tartari +

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Graphene Plus: reusable eco-innovative sorbent for oil spills clean-up and polluted water treatment Annalisa Pola, Giulio Cesareo, Gianni Tartari + Directa Plus S.p.A., Via Cavour 2, 22074 Lomazzo, (CO) + IRSA-CNR, UOS Brugherio, Via del Mulino, 19, 20861 Brugherio (MB)

DIRECTA PLUS COMPANY PROFILE WHAT WE DO Directa Plus is a technology company pursuing the development of innovative processes for the production of engineered graphene based materials (G+ process) and metal nanostructures (D+ process). ABOUT US Directa Plus SpA is an Italian Limited Company, headquartered in Lomazzo (Como), founded in 2005. Company demonstration units are located in Lomazzo (Como) and in Ulm (Baden Württemberg). PARTNERS We actually collaborate with more than 20 industrial companies and academic organization, in 8 macro application areas.

DIRECTA PLUS WATER TREATMENT WATER TREATMENT Since 2011 Directa Plus has sustained research activities on graphene based materials application in water treatment sector. COLLABORATIONS In 2011-2012 Directa Plus has performed a research activity on G+ products use in polluted water treatment with: We actually collaborate with some industrial companies in water treatment sector.

WHAT IS GRAPHENE? Exceptional chemical and physical properties: High surface active area (>2500 m2/g); Possibility of functionalization. Pristine or functionalized graphene can be actually produced only at laboratory level, with high costs methods and with low production yield

DIRECTA PLUS PRODUCTS: G+ MATERIALS GRAPHENE BASED MATERIALS Interesting chemical and physical properties HIGH VOLUME PRODUCTION Actual production capacity: 5 tonnes per year 2014 production capacity: 20 tonnes per year PROCESS BENEFITS Simple Scalable Low costs Environmental friendly Patented

DIRECTA PLUS PRODUCTS: G+ MATERIALS We produce 4 types of graphene based materials Basic G+ Ultra G+ Liquid G+ Pure G+ G+ materials have high affinity for organic pollutants We first tested Basic G+ for oils and hydrocarbons removal from water

GRAPHENE PLUS FOR OIL SORPTION

WHAT IS BASIC G+? 1. Natural Graphite 2. Graphite Intercalation 3. Graphite Super Expansion Basic G+: SEM image. Typical accordion-like structure of expanded graphite.

BASIC G+ FOR OIL SORPTION: TEST PERFORMED ENGINE MINERAL OIL CRUDE MINERAL OIL UNLEADED PETROL AND DIESEL LOW-MEDIUM-HIGH VISCOSITY G+ POTENTIAL Oil spills clean-up activities Hydrocarbon removal at LOW CONCENTRATION (from mg/l to µg/l)

RESULTS: ADSORPTION vs SALINITY 100 Oil adsorbed by 1 g of G+ (g) 90 80 70 60 50 40 30 20 10 0 Type of oil Basic G+ adsorption is not influenced by water salinity

RESULTS: ADSORPTION vs TEMPERATURE 100 Oil adsorbed by 1 g of G+ (g) 90 80 70 60 50 40 30 20 10 0 Temperature ( C) <15 API 30-40 API > 40 API Basic G+ adsorption is influenced by temperature and oil viscosity

SORBENT AND OIL RECOVERY: TEST PERFORMED Recovery of Basic G+ Inceneration at least for 3 cycles Recovery of sorbed oil Mechanical squeezing more than 80% of oil is recovered Solvent extraction at least 1 cycle with the recovery of 97% of sorbed oil Recovery of both Basic G+ and sorbed oil Steam stripping Other techniques Thermal desorption Filtration under mild suction Centrifuge

RESULTS: TOXICOLOGICAL TESTS Toxicological tests on Artemia franciscana (96 h test; APAT IRSA-CNR 8060 2003) Toxicological tests on Daphnia magna (24 h test; APAT IRSA-CNR 8020b 2003) G+ Basic has recently been approved by the Italian Environmental Ministry as an inert sorbent material that can be used in sea oil spills clean-up activity.

(Basic) GRAPHENE PLUS ADVANTAGES Basic G+ is chemically inert, non-toxic, non-inflammable, hydrophobic and insoluble in water (it does not sink); Basic G+ performs at least 4 times better than traditional sorbent material actually on market. Basic G+ is completely recyclable and guarantees the recovery of sorbed oils through different methods; Basic G+ has a cost/efficiency completely comparable with the best sorbent products on the market. Basic G+ can be produced directly on site.

GEnIuS - ECOINNOVATION - THE PROJECT Graphene Eco Innovative Sorbent Grant Agreement - Eco/12/332920

GEnIuS - ECOINNOVATION - OBJECTIVES OVERALL OBJECTIVE To penetrate the European market and to launch Graphene Plus as eco-innovative sorbent for oil spills clean-up activities. SPECIFIC OBJECTIVES To replace the traditional existing oil spill sorbents and dispersants with an eco-innovative solution based on graphene, in order to limit the use of chemical products and reduce the impact on natural ecosystems and human health; Drastically to minimize the production of waste deriving from an oil spillage area thanks to the recovering capacity of both sorbed oil and G+. To make oil industries and stakeholders aware of the potential of G+ as an oil sorbent material and stir their interest in using it.

GEnIuS - ECOINNOVATION WORK PACKAGES GEnIuS foresees the realization of pilot test in local contaminated areas, with the collaboration of public and private partners and end-users. Provincia and Comune of Como have expressed their interest for GEnIuS project. Rumanian Environmental Ministry will be involved in pilot test activities of the project.

GEnIuS - ECOINNOVATION WORK PACKAGES We are collaborating with an industrial partner for the containment of loose Basic G+ inside booms and pads We are searching for other partners to test Basic G+ in real life applications

G+ MATERIALS: WATER TREATMENT POTENTIAL G+ materials have high affinity with organic pollutants Performed preliminary laboratory tests on: Pesticides PBDE (Polybrominated Diphenyl Ethers) Chlorinated solvents Dyes (Reactive Red)

AIR TREATMENT: LABORATORY & FIELD TESTS In collaboration with Polytechnic of Milan and an industrial partner (waste incineration plant) we will test G+ materials for PAHs and dioxins removal from air.

THANK YOU FOR YOUR ATTENTION! Please visit our new web-site: www.directa-plus.com