tallinn university of technology estonian oil shale ash as raw material for manufacturing glass...
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Tallinn University of Technology
ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS
Rein KUUSIK
Laboratory of Inorganic Materials, Tallinn University of Technology, Tallinn, Estonia
Mauro MARAGNONI, Enrico BERNARDO
Dipartimento di Ingegneria Industriale, Universita` degli Studi di Padova, Padova, Italy
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Location of Estonia in Europe
Estonia
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Main Estonian
natural resources are
phosphorite
and
oil shale
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Estonian Oil Shaleresource for oil, energy and chemicals
We can produce from 1 ton of Estonian oil shale:
From 1 ton of
oil shale
(2030 kcal/kg)
125 kg of shale oil (9 500 kcal/kg)35 Nm³ of retort gas (11 200 kcal/m³)
850 kWh of electricity
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AS Narva Elektrijaamad
AS NARVA ELEKTRIJAAMAD
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Formation of ash
Circulated fluidized bed combustion
(CFBC) •BA (bottom ash) ~30%•INT (Intrex ash) ~11%•ECO (economizer ash) ~6%•PHA (air preheater ash) ~3%•ESPA ~50%
Pulverized firing (PF) •BA (bottom ash) ~40%•SHA (superheater ash) ~3%•ECO (economizer ash) ~5 %•CA (cyclone ash) ~35%•ESPA (electrostatic precipitator ash)~17%
BA SHA ECO CA ESPABA INT ECO PHA ESPA
t=720-800oCkCO2 = 0,65-0,75
t=1250-1400oC, kCO2 = 0,97
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Characterization of oil shale ashes CFBC ash PF ash
Lime CaO 3.2-19.9% 14.3-29.3%
Periclase MgO 3.3-7.0% 3.8-7.9%
Melilite (Ca,Na)2(Mg,Al)(Si,Al)3O7 1.0-3.6% 3.2-18.9%
Merwinite Ca3Mg(SiO4)2 3.0-5.2% 6.5-13.2%
Belite Ca2SiO4 4.6-7.3% 12.3-20.3%
Wollastonite CaSiO3 1.4-3.4% 0.7-2.6%
Orthoclase, KAlSi3O81.3-15.6% 1.7-9.7%
Quarz SiO2 5.6-17.7% 1.6-10.4%
Calcite CaCO3 4.0-34.8% 2.0-7.6%
Anhydrite CaSO4 8.8-29.9% 4.6-24.1%
more lime and secondary silicates
more calcite and anhydrite
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Oil Shale Ash Utilization Prospects
5 – 7 mln t/yearof ash
Backfilling at mining, 1
Building materials, 2
Road construction, soil stabilization, 3
Agricultural use: soil liming, 4
Sorbents for phosphorus capture, 5
Filler for polymers, 6
New products: PCC and sorbents, 7
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The present work
aims at evidencing the feasibility of a sintering approach for the production of strong and chemically stable
glass-ceramics, based on glass frits.
The impact of binders (of organic or inorganic nature),used to favour the shaping of fine powders, and recycled glass powders, considered in order to improve the chemical stability of the sintered bodies, has been also discussed.
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SEM image of glass-ceramics from: (a) ASH2 with Kaolin; (b) ASH2 with PEG
Details of sintered ceramics from the ASH2 glass with borosilicate glass: (a) visual appearance; (b) high magnification SEM image
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Conclusions
o Selected kinds of Estonian oil shale ash may be employed as the main raw material (being used in an amount exceeding 60%) in the formulation of waste-derived glasses, to be converted into glass-ceramics
o Sinter-crystallization, found to be active for the investigated compositions, allowed the obtainment of glass-ceramics by very fast and cost effective firing treatments (temperatures <1000°C, holding time of 30 min, fast heating)
o Optimized formulations, in terms of composition and selection of binders, led to strong glass-ceramics with a high reliability (Weibull’s modulus >10)
o The chemical stability of the sintered glass-ceramics may be improved by mixing waste-derived glass with recycled borosilicate glass.
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Thank You!
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