Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS...

12
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 [email protected] , [email protected] , [email protected]

Transcript of Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS...

Page 1: 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

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

[email protected], [email protected], [email protected]

Page 2: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 2

Location of Estonia in Europe

Estonia

Page 3: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 3

Main Estonian

natural resources are

phosphorite

and

oil shale

Page 4: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 44

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

Page 5: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 5

AS Narva Elektrijaamad

AS NARVA ELEKTRIJAAMAD

Page 6: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 6616.12.2008

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

Page 7: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 7

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

Page 8: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 8

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

Page 9: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 9

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.

Page 10: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 10

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

Page 11: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 11

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.

Page 12: Tallinn University of Technology ESTONIAN OIL SHALE ASH AS RAW MATERIAL FOR MANUFACTURING GLASS CERAMICS Rein KUUSIK Laboratory of Inorganic Materials,

April 17, 2015 Kuusik-Maragnoni-Bernardo, SVS2015 12

Thank You!

12