Laboratoire Matériaux et Durabilité des Constructions - PDF

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Laboratoire Matériaux et Durabilité des Constructions Université de Toulouse INSA - UPS Toulouse France INSA Génie Civil - 135, Avenue de Rangueil Toulouse Cedex

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Laboratoire Matériaux et Durabilité des Constructions Université de Toulouse INSA - UPS Toulouse France INSA Génie Civil - 135, Avenue de Rangueil Toulouse Cedex 4 1 WASCON 2009 Synthesis of binders using waste materials 3-5 June 2009, Lyon (France) Toulouse, France Martin Cyr, Pierre Clastres, Marie Coutand Laboratoire Matériaux et Durabilité des Constructions Jean-Marc Balandier Yann Rousseau Pierre Silvestre, consultant 2 Introduction and objectives Industrial processes large quantities of mineral-rich waste often rich in silicon and calcium water treatment sludge paper-manufacturing sludge limed sludge foundry sands etc. 7Mt in USA + 10Mt in EU tons of dry materials in France in 2002 Most of these wastes are at present sent to landfills spread for agricultural purposes incinerated 3 4 Introduction and objectives Recycling of industrial and institutional waste rich in mineral resources for the manufacture of binders, while saving on natural resources (clay and lime) recycle wastes containing large amounts of mineral resources, in order to synthesize hydraulic binders at temperatures not exceeding 1000 C 5 Phases of the project and principal results Project divided into 4 phases: Construction of a database of waste resources; Selection in the laboratory of combinations of wastes for the synthesis of binders; Industrial scale tests carried out in a rotary furnace; Validation of the results in an industrial application (road test). 1- Construction of a database of waste resources Aim: to establish a list of characterised wastes locally available and liable to enter into the formulation of binders 44 residues identified and characterised Technical files for each residue Approximate composition (CaO, SiO 2 ) Sample reception Compatibility With binder production Example: quantity 500 tons/year yes Exhaustive analyses Waste availability (quantity, distance, cost) no Other application Physical properties - particle size distribution - specific surface area - water content Chemical properties - major and minor elements (including heavy metals) Mineralogical properties - structure and composition Environmental behaviour - leaching Database 6 FICHE DE CARACTERISATION PRODUIT Analyse par FLUORESCENCE X (rapport massique) Info générales: Société: Adresse: CP/Ville: Activité: Contact: Fonction: téléphone: fax: Appellation produit: Analyse par DIFFRACTION X (rapport massique) Référence: Tonnage: CODE EU: Phase minéralogique % Aspect physique: Traitement actuel: Analyses ARF Analyses Physico-Chimique % Cl: Matières séches (110 c -3h): % H2O: Perte au feu (1100 c - 1h): % S: PCS (kcal/kg): Métaux lourds: Alcalins (mg/l): mg/l As: Pb: Ca: Cd: Sb: K: Co: Se: Na: Cr: Sn: Cu: Te: Hg: Tl: Mn: V: Pb+Cr+Sn ( 10.000): 0 Ni Zn: Sb+As+Co+Ni+V+Te+Se ( 3000): 0 Surface de Blaine: Observation: Lixiviation: mg/l (sur M.S) As: Cu: Pb: Ba: Hg: Sb: Cd: Mo: Se: Cr: Ni: Zn: Granulométrie: masse cumul tamis tamis 2 0 tamis tamis tamis bol Courbe granumomét rique 0.08 Produit retenu pour formulation: oui non Date: 7 Selection of wastes based on several criteria Amount of residue available 500 tons/year Approximate composition (CaO, SiO 2 ) Sample reception Waste availability (quantity, distance, cost) Chemical composition - Calcium and silicon - Other such as alkalis, known for reducing the melting point of materials Mineralogical form - Calcium and silicon potentially available: calcite (Ca), glass (Si), quartz (Si) Heavy metal contents - Hg alone 10 ppm (10 mg/kg) - Cd + Hg + Ti 100 mg/kg - Sb + As + Cr+ Co + Ni+ V + Sn + Te + Se 1% Compatibility With binder production Example: quantity 500 tons/year yes Exhaustive analyses Physical properties - particle size distribution - specific surface area - water content Chemical properties - major and minor elements (including heavy metals) Mineralogical properties - structure and composition Environmental behaviour - leaching Database no Other application 8 Counts 2- Selection in the laboratory of combinations of wastes for the synthesis of binders CS CS C 2 F CS Quartz Free lime +. + C 2 F Aim: to select specific combinations of wastes in order to burn them in a laboratory muffle oven b-c2 S 500 X-ray diagram of a belite binder synthesised in the laboratory q Ka Co 9 10 Table 1 Minerals present in synthesised binders at laboratory and industrial scales Lime-based binders Belite-based binders Laboratory Industrial Laboratory Industrial Range of free lime content (CaO) 75-80% 50-60% 2-28% 13-36% Range of belite content () 0-5% 12-16% 18-75% 13-16% Impurities reactive* Periclase MgO Anhydrite CaSO Portlandite Ca(OH) Impurities inert** Quartz SiO Calcite CaCO Wollastonite CaSiO Perovskite CaTiO Gehlenite Ca 2 Al 2 SiO Hematite Fe 2 O : 10%; 5% +++ 10%; 2% ++ 5%; +: 2% * considered as active in basic environment; ** considered as inert in basic environment 3- Industrial scale tests carried out in a rotary kiln Tests in a 60m-long, 3.2m-diameter rotary kiln Temperature of around 1000 C For each test, approximately 50 tons of mineral residues Fraction of the fuel replaced by a highly calorific residue 11 12 Table 1 Minerals present in synthesised binders at laboratory and industrial scales Lime-based binders Belite-based binders Laboratory Industrial Laboratory Industrial Range of free lime content (CaO) 75-80% 50-60% 2-28% 13-36% Range of belite content () 0-5% 12-16% 18-75% 13-16% Impurities reactive* Periclase MgO Anhydrite CaSO Portlandite Ca(OH) Impurities inert** Quartz SiO Calcite CaCO Wollastonite CaSiO Perovskite CaTiO Gehlenite Ca 2 Al 2 SiO Hematite Fe 2 O : 10%; 5% +++ 10%; 2% ++ 5%; +: 2% * considered as active in basic environment; ** considered as inert in basic environment industrial tests less efficient in producing lime and b-c2s phases Main reasons explaining these results 13 Large diameter of some calcareous products at the entrance of the kiln formation of free lime aggregates which were not broken down during the burning process lime deficit in the kiln and the production of wollastonite (CS) instead of. Part of the lime consumed by the titanium present in the highly calorific residue formation of perovskite (calcium titanate), which is very stable at room temperature and in a basic environment Temperature below 1000 C in the kiln explain the large quantities of unreacted minerals still present in the binders 4- Validation of the results in an industrial application (road test) Aim: to qualify the synthesised binders in a road-work test asphalt gravel waterproof membrane treated embankment geotextile gravel drain Profile of road structure for the test of lime-based binder used in treated embankment. Experimental road structure built on the production site of the binders 48m 2 and 0.6m depth Built in November 2008 Will be studied for 12 months Mechanical tests carried out Percolate water periodically analysed 14 Construction of the road structure for the test of lime-based binder (used in treated embankment). 15 16 (Partial) results of percolation L / S L/S CHROME VI L/S L/S Conclusion Aim of the project: to produce binders from mineral-rich waste Database: 44 residues identified and characterised Selection of combinations (laboratory scale): lime-based binders: belite-based binders: high lime contents (+ periclase and anhydrite) 18-75% of Industrial scale tests - less efficient in producing lime and b-c2s phases - problems identified : particle size of waste materials, low burning temperature, parasite reactions in the kiln. Industrial application (road test) Monitoring in progress 17 18 Project financially supported by the European Union via the LIFE programme Synthesis of binders using waste materials Martin Cyr, Pierre Clastres, Marie Coutand ; Laboratoire Matériaux et Durabilité des Constructions Jean-Marc Balandier Yann Rousseau Pierre Silvestre
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