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Melting and Fining Processes in Industrial Glass Furnaces IMI-NFG

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Melting and Fining Processes in Industrial Glass Furnaces IMI-NFG IMI-NFG Course on Processing in Glass Spring 2015 (available online www.lehigh.edu/imi) Lecture 2: Melting and Fining processes in industrial glass furnaces Mathieu Hubert, PhD CelSian Glass & Solar Eindhoven, The Netherlands [email protected] Introduction • In Lecture 1, the preparation of the batch has been described, from the selection of the raw materials to the charging of the batch in the furnace via the doghouse (or day-hopper) • The batch is introduced in the furnace at high temperature, and the energy provided to the batch is used to convert the batch into a glass melt • The batch-to-melt conversion implies a series of chemical reactions (decarbonation, dehydration, solid-state reactions, formation of low-melting eutectics, dissolutions) • This lecture will highlight these different reactions and processes, from the introduced batch to an homogeneous and bubble-free glass melt (before the forming processes) IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 2 Outline of this lecture 1. Melting of the batch From the batch to the melt Chemical reactions Sand dissolution 2. Fining of the melt Dissolved gases Fining mechanisms Removal of bubbles and seeds IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 3 Schematic of an industrial glass melting tank * This is a schematic representation, but many different furnace designs exist (more on that in Lecture 3) IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 4 Melting and fining in the furnace Batch blanket Melting and sand dissolution Primary Secondary fining fining (refining) IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 5 Melting and fining in the furnace Batch Batch input ≈ 1200 Kg 25°C Rough melt Batch melting ≈ 1001 Kg 1200°C Sand grain Seedy melt ≈ 1001 Kg dissolution 1400°C Clear melt Fining ≈ 1000 Kg 1500°C Refining and Conditioned melt 1000 Kg conditioning 1250°C Inspired from R. Conradt, Thermodynamics and Energy Demand for Batch-to-Melt Conversion, presented at the 6th ICG summer school, Montpellier, France, July 2014 IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 6 Melting and fining in the furnace Batch Batch input ≈ 1200 Kg 25°C Relatively fast (~ 1h) Rough melt - Batch melting ≈ 1001 Kg 1200°C Requires significant energy input Sand grain Seedy melt ≈ 1001 Kg dissolution 1400°C Longer process (~ 24h) Clear melt Fining ≈ 1000 Kg 1500°C - Requires significant lower energy input Refining and Conditioned melt 1000 Kg conditioning 1250°C Inspired from R. Conradt, Thermodynamics and Energy Demand for Batch-to-Melt Conversion, presented at the 6th ICG summer school, Montpellier, France, July 2014 IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 7 Batch melting-in • The melting-in process occurs mainly by reactions within the batch blanket forming liquid phases. • In the heated batch piles or blanket: The first aggressive melt phases are formed, which will strongly attack and largely dissolve the components that are difficult to dissolve, like quartz sand or feldspar/china clay particles. The melt phases thus formed flow from the batch blanket area into the glass melt. So the batch blanket becomes increasingly thinner Still some of the non-dissolved sand particles will arrive in the glass melt itself, where these particles will have to dissolve further by diffusion of SiO2 in the molten glass, away from the sand grain surface. IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 8 Melting process of the batch blanket combustion space heat transfer gas release reaction zone figure 1b glass melt layer temperature profile thick- glass ness normal batch level reaction zone glassmelt figure 1c flow heat transferred From Ungan and Viskanta, "Melting Behavior of Continuously Charged Loose Batch Blankets in Glass Melting Furnaces", Glastechische Berichte, 59 (10), 1986, pp. 279-291 IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 9 Detailed representation of batch melting process 1500 o C Layer glassmelt melts Dissolution loose batch sand grains sand grains gas melting melting reactions reactions carbonates (soda/lime) dissolution sand gas grains batch sand grains glass melt 1400 o C b. top of batch blanket c. bottom side of batch blanket From Ungan and Viskanta, "Melting Behavior of Continuously Charged Loose Batch Blankets in Glass Melting Furnaces", Glastechische Berichte, 59 (10), 1986, pp. 279-291 IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 10 Different steps of the melting process • Melt reactions • Melt energy (enthalpy of heating the batch and decomposition melting/fusion reactions) • Melting kinetics / heat transfer • Melting parameters: effect of the temperature grain size (especially for sand and alumina raw materials) glass composition IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 11 Melt reactions IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 12 Melting reactions • De-hydration of some raw materials and water evaporation • Solid state reactions between individual raw materials • Formation of primary melt phases and melting of alkali rich carbonates. (typically in the temperature range: 700-900°C) • Dissociation or decomposition reactions of Ca- and Mg- containing carbonates (e.g. limestone and dolomite), resulting in development of CO2-gas. (Temperature range 500-1000°C) (Na2CO3 will not decompose spontaneously, but reacts with sand or limestone). • Dissolving of the SiO2 in the alkali rich carbonate melt phases, typically above 1000°C. Sand reacts between about 750-1000°C with sodium silicates or soda to form liquid sodium silicates (associated with the release of CO2-gas when limestone or soda or dolomite is reacting with sand) IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 13 Dehydration • Takes place at ± 100°C for physically bonded water • In case of clay in the batch, de-hydration may occur up to 650- 700°C • Dehydration (water evaporation) is very energy intensive, and it is represents an important part of the total energy consumption IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 14 Sand dissolution • Pure silica melts at very high temperature (> 1700°C) • In standard glasses (except e.g. pure silica glass) sand is incorporated in the glass melt by dissolution, and not by melting • Sand dissolution is a critical step in industrial melting process • It is highly dependent on the initial grain size distribution of the sand grains in the batch, as well as the presence of aggressive molten phases (e.g. alkaline phases) • Sand grains react with other batch components or dissolve in the obtained melt in most glass melting processes. The optimum grain size depends on the glass type. IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 15 Grain size distribution of quartz sand, recommended for different applications, values in mass% Application Indication Grain size (mm) Size class <0.03 <0.06 <0.125 <0.25 < 0.35 <0.5 <1.0 Container glass Coarse - - 1 25 55 75 95 sand Container & Float Medium - - 10 50 75 95 100 sand Float glass Fine sand - 1 5 70 85 100 100 Float glass Very fine 3 15 85 100 100 100 sand E-glass & alkali- Coarse 40 70 95 100 100 100 100 borosilicate silica powder E-glass Medium 70 95 99 100 100 100 100 silica powder E-glass Fine silica 98 100 100 100 100 100 100 powder IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 16 Solid-state reactions in the batch • Solid-state reactions can be divided into two routes: the carbonate route and the silicate route • The carbonate route (path) is characterized by reactive dissolution of silica sand with a binary melt phase of soda ash and limestone below about 900°C. Soda ash and limestone, in contact with each other, may form a double carbonate by a solid state reaction forming the species Na2Ca(CO3)2 • At about 820°C, this intermediate reaction product starts to melt and becomes suddenly more reactive (better contact) towards silica sand grains. • Silica reaction with Na2Ca(CO3)2 forms a viscous Na2O·CaO·SiO2 melt plus CO2 gas. IMI-NFG Course on Processing of Glass - Lecture 2: Industrial glass melting and fining processes [email protected] 17 Solid-state reactions in the batch • The silica/silicate route is based on eutectic melting of a mixture of components, including the sodium disilicate phase, formed by solid state reactions between sand and soda. • The eutectic melting of SiO2 and Na2O·2SiO2 takes place at 799°C and silicate rich melts are formed. • The degree to which these reactions occur depends on the mutual contact between the components. Within a compacted batch
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