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Mousses de verre issues du recyclage : Quelques exemples d’études et applications Ronan LEBULLENGER et al. ronan.lebullenger@univ-rennes1.fr UMR6226 - ISCR – Eq. Verres et Céramiques. France. ISCR Expertise Conception & Synthesis of Molecules & Materials
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Mousses de verre issues du recyclage: Quelquesexemplesd’études et applications Ronan LEBULLENGER et al. ronan.lebullenger@univ-rennes1.fr UMR6226 - ISCR – Eq. Verres et Céramiques
France ISCR Expertise Conception & Synthesis of Molecules & Materials with Dedicated Properties Chemistry & Engineering for Sustainable Development Molecules &Materials for Optics & Electronics Molecules & Materials for Health Rennes Institut of Chemical Sciences ISCR
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
3R management for glass • The 3Rs represent a strategy for the management of end-of-life products and the resulting waste: • Reduce the amount of products that arrive at the end of life, • Reusing products or parts thereof that would otherwise become waste, • Recycle raw materials. • End-of-life products that can not fit into this scheme are considered ultimate waste, they can only be stored, eventually waiting to find a way to return them to the circuit.
By Optimisation of: melting conditions - homogeneity, stone and bubblefreegob, parison viscosity,...) shaping containers process - mould and press conditions) coating - spray in cold section and annealing kiln • better mechanical properties for lighter products
Definition of glass from environmental agencies CAS Number for glass: 65997-17-3 Glass, oxide, chemicals CAS Number: 65997-17-3 EPA Registry Name: Glass, oxide, chemicals Molecular Formula: Unspecified
From EPA , United States Environmental Protection Substance Registry Services (SRS). Oxides of the first seven elements listed* comprise more than 95 percent, by weight, of the glass produced: Aluminum*; Boron*; Calcium*; Magnesium*; Potassium*; Silicon*; Sodium*; Antimony; Arsenic; Barium; Bismuth; Cadmium; Carbon; Cerium; Cesium; Chromium; Cobalt; Copper; Germanium; Gold; Holmium; Iron; Lanthanum; Lead; Lithium; Manganese; Molybdenum; Neodymium; Nickel; Niobium; Nitrogen; Phosphorous; Praseodymium; Rubidium; Selenium; Silver; Strontium; Sulfur; Tellurium; Tin; Titanium; Tungsten; Uranium; Vanadium; Zinc; Zirconium RoHS (Register of Hazardous Substance) REACH =Enregistrement, évaluation, autorisation et restriction des substances chimiques en anglais : Registration, Evaluation, Authorization and restriction of CHemicals (REACH)
Glass containers collect • (volunteer contribution points) Separated colours (Germany, UK, etc..) Mixed colours (France, ...)
Specifications for sorted and processed cullet to be accepted for secondary raw materials in glass production
The third R step in the 3Rs approach of glass end-consumer life is the recycling. Two ways are possible: the closed-loop recycling where glass waste (cullet or internal cullet) is considered as secondary raw-materials, the open-loop process where glass waste is considered as an additive or a matter to transform before re-using.
Benefits of recycling glass (close-loop) • Energy savings. An increase of 10% of recycled glass in place of virgin raw materials allows a 3% energy saving, as an example, increasing the cullet % in the batch of an efficient end-port fired regenerative container glass furnace from 65 up to 75 % decreased the specific energy consumption from 3.95 MJ/kg molten glass to 3.8 MJ/kg. The use of cullet also aids in reducing batch-free time by both reducing the amount of refractory material in the batch, and by providing additional liquid throughout the melting process; • Limiting the release of CO2. One ton of recycled glass saves more than 500 kg of CO2; • Decreasing the removal of natural resources. For each kg of cullet used in replacement of the raw material, is a saving of 1.2 kg for virgin materials; • Optimizing logistics and thus minimizing the carbon footprint linked to transportation. Recycled glass comes from local collections, close to the glass production plants; • Avoiding landfilling or incineration
Industrial and Academic Research for Glass Recycling (WoS April 2016)
Why recycling cullet and CRT ? • Industrial glass wastes (Soda lime silicate SLS): • Cullet from container glass or tableware (! colour) • Automotive glass • Windshield car (! PVB) • Lateral windows (! enamels) • Glass balls for elastomercuring in Ballatonibed • Waste Electrical and Electronic Equipment - WEEE • Microwave furnace glass plate, fridge glass shelf • (! heavy metal contain or contamination during dismantling) • LCD screen • CRT (Pb (funnel), Ba (panel), containing) • The glass waste treatments have a cost: • Collect, wash and control the cullet composition (metal particle, ceramic stones…) for a re-use in batch melt for container glass (SLS) (100€/ton) • Landfilling: 50€/ton for non-hazardous (SLS), more than 150€/ton for hazardous (CRT) • What about “alternative” and/or “durable” routes ?
Waste glass resources Window glass Container glass Televisions - Cathode ray tube Lamp glass
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
Mixed crushed panel and funnel CRT glasses + fondant for lowering viscosity (alkaline, earth-alkaline carbonates) + reducing agent (C) = “New” Glass + precipitate Pb° metal T°, time • Lead oxide reduction schema • Lead beads from CRT glass • Unleaded Glass • [Pb]<0,05 wt%
Foam glass with unleaded glass or panel glasses • Elaboration • Expansion • Heattreatment • Formation of gasbubbles (CO2 or N2) • Glass waste • Foaming agent • + • Glass foam Temperature • Glass waste • CRT: Cathode Ray Tube glass • SLS: Soda-Lime Silicate glass • Operating temperature • Cooling phase Time • Foaming agent • AlN, CaCO3, SiCor C • Temperature ramp Furnace temperature vs. time
T = 850°C foaming particles Glass cullet N2, CO2bubbles foaming agent decomposition or reaction Reactiveviscousmolten glass foaming particles
Gas production • 2 AlN (s) → Al2O3 (s) + N2 (g) • 4 AlN(s) + 3 TiO2 (s) → 2 Al2O3 (s) + 3 TiN (s) + ½ N2 (g) • TiN (s) → TiO2 (s) + ½ N2 (g) • SiC (s) → SiO2 (s) + CO, CO2 (g) • CaCO3 (s) → CaO (s) + CO, CO2 (g) • NB: These reactions for gas production are dependent of redox equilibria
Tunning open / closed porosity CRT + %x AlN + %y TiO2 @ 850°C Closed porosity (%) Open porosity (%) • Open porosity Filtration, draining application • Closed porosity Insulation application
Glass foam beads synthesis Granulator: rotary plate
granulate of foam glass characteristics * Calculée dcomp=dapp x 0,7 ** Compression sur bloc # Estimée
Unleaded glass [Pb]<500 ppm Unleaded or panel glasses valorised in foam materials
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
Recycled glass foams for high power microwave terminations • Collaboration with IETR UR1 - UBO • Compare inorganic foam • carbon charged with polymer
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
Common silicate glasses for catalytic applications • Foam glass as support for metal nanoparticles • (Ru, Rh, Pd, Au….) • Oxidation catalysis for Volatile Organic Compounds • degradation or contaminated water
Common silicate glasses for catalytic applications • Good impregnation • of NP aggregates (2-5 nm) • without • the use of de g-Al2O3washcoat • as used for ceramic or metal foams • lixiviation test by soxhlet method
Common silicate glasses for catalytic applications • Water treatment by advanced oxidation • Coupling with ozone (O3) for aqueous solution • Formation of radicals HO° verypotents at ambiant T and P • Mineralisation of micro-pollutants • Drug residues, endocrine disruptors, pesticides, etc • Potabilization or purification • Air treatment by advanced oxidation • Coupling with ozone (O3) for gaseous solution • Mineralisation of micro-pollutants • Industrial air treatment • Indoor air treatment Half-life time of atrazine / 10 Decomposition of O3 with concomitant degradation of isopropanol and toluene demonstrated
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
Biomaterials from clear glass cullet 75SiO2 -15Na2O - 10CaO (wt%) for flint glass SLS 46 SiO2 - 24 Na2O - 24 CaO- 6P2O5 (wt%) for 46S6 Hench glass • Compare SLS foam with 46S6 • Check the cytotoxicity of SLS foam • - on bone cells SaOS • - on endothelial cells EAHY926 Figure 5(a) Figure 5(b) SaOS micrograph EAHY 926 micrograph
SJ008 SJ010 SJ009 • Raw materials for 46S6 synthesis • SiO2, CaCO3, NaPO3.3H2O, Na2CO3 , CaSiO3 • Raw materials for foam samples • SLS flint glass powder • CaCO3 —> CaO + CO2 • (MAP) 2NH4H2PO4 —> 2NH3 + P2O5 + 3H2O • (DAP) 2(NH4)2HPO4 —> 4NH3 + P2O5 + 3H2O SJ011 SJ001 SJ012 Foamsamples and 46S6 bulksamples
MTT test 46S6 best biocompatibility Foam (SLS+CaCO3 ) not so bad... MAP and DAP foams present low biocompatibility, ? The presence of residue of NH4 is may be responsible ? .
3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences
Glass recycling: a linkbetween Arts and Sciences • EESAB, École européenne supérieure d'art de Bretagne
Undergrate and graduate students who participated Fabien BOIVENT (IUT SGM St Brieuc) - Nicolas FRESLON (IUT Chimie Rennes) , Margot TITOURAIS (IUT Chimie Rennes) , Thibault REYNALDO (L3 Chimie Rennes) , Manu GAUTIER (M1 Chimie) , Laure MOUGENOT (L3 Chimie Rennes) , Alexis MORIN (L3 Chimie Rennes) , Sébastien GENTY (L3 Mag. Matériaux Rennes) , Laure CERCUEIL (IUT Chimie Rennes) , Marc-Antoine THUAL (L3 ESIR1 Rennes) , Clyde MIDELET (L2 Phys Chimie Lorient) , Jade LEMOINE (M1 MEF Rennes) , Pierre ANDORIN (IUT Chimie Rennes) , Youenn POINTEL (ESIR1) , Sébastien GENTY – Ingénieur Etudes R&D (CDD) , Geoffrey LOUVET (IUT Chimie - Prod) , Thibaud BREGENT (L2 PCSTM UR1) , Laure CERCEUIL - Ingénieur Etudes R&D (CDD) , Aymeric HEDREUL - IUT Chimie Rennes , Guillaume LANOE - IUT SGM St Brieuc UR1, Killian DENOUE - L3 Chimie UR1, Valentin AUDEBERT, M2 Quatro – ENSCR, Anthony PIEL - IUT SGM UR1 , Shuyue JI - IUT Chimie ORSAY , Alan MATEU - ESIR1 UR1 , Steven AKOUN, Sarah MONTEUIL et al. EESAB • All colleagues (Recyver, V&C, ISCR, IPR, ...) Thanks Merci Natural granite from Brittany Or Foam glass ?