mineral composition of ash using x-ray...
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1TU Bergakademie Freiberg I Institut für Energieverfahrenstechnik und Chemieingenieurwesen
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Institutsname
Mineral composition of ash using X-ray diffractometry
Leipzig, 21st May 2012
Monika Kurková, Sabine Starke
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Mineral - naturally occurring solid chemical substance- has characteristic chemical composition - ordered atomic structure (crystalline structure)- specific physical properties
X-ray diffractometry - non destructively method of phase analysis - in combination with temperature/pressure chamber
in situ investigation of phase formations, decompositions and changes of crystalline matter
Introduction
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Mineral - naturally occurring solid chemical substance- has characteristic chemical composition - ordered atomic structure (crystalline structure)- specific physical properties
X-ray diffractometry - non destructively method of phase analysis - in combination with temperature/pressure chamber
in situ investigation of phase formations, decompositions and changes of crystalline matter
Introduction
Lignite ash investigation - ash mineral composition- temperature influence on mineral composition - pressure influence on mineral composition- thermogravimetry
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X-ray devices & Temperature/pressure chamber
S4 PIONEER S8 TIGER D8 DISCOVER with GADDS and TCP20
Temperature/pressure chamber TCP 20
Beryllium window Temperature range (30 °C to 1000 °C) Pressure up to 20 bars Ta, Pt/Rh heating stripWater cooling Turbomolecular pump for vacuum
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Applications- Ash/slag investigation
- Pipe corrosion investigation
- Deposits, sediments phase analyses
ash deposits - micro combustion reactor
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Applications
ash/slag film
slag piece
cooling pipe corrosion
- Ash/slag investigation
- Pipe corrosion investigation
- Deposits, sediments phase analyses
ash deposits - micro combustion reactor
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Applications
ash/slag film
slag piece
cooling pipe corrosion
- Ash/slag investigation
- Pipe corrosion investigation
- Deposits, sediments phase analyses
Ash 1 – 815 °C Ash 1 – 1100 °C
Ash 2 – 815 °C Ash 2 – 1100 °C
Ash 3 – 815 °C Ash 3 – 1100 °C
ash deposits - micro combustion reactor
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ashing temperature - 450 °C
Na-rich Si-poor lignite ash sample analyses
Oxides/ Conc.Element Mass %CO2 12.52
Na2O 6.20MgO 13.91Al2O3 1.16
SiO2 1.15
SO3 23.70Cl 0.60K2O 0.50CaO 31.50Fe2O3 7.96Traces 0.80Sum 100.00
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ashing temperature - 450 °C
Na-rich Si-poor lignite ash sample analyses
Oxides/ Conc.Element Mass %CO2 12.52
Na2O 6.20MgO 13.91Al2O3 1.16
SiO2 1.15
SO3 23.70Cl 0.60K2O 0.50CaO 31.50Fe2O3 7.96Traces 0.80Sum 100.00
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ashing temperature - 450 °C
Na-rich Si-poor lignite ash sample analyses
Oxides/ Conc.Element Mass %CO2 12.52
Na2O 6.20MgO 13.91Al2O3 1.16
SiO2 1.15
SO3 23.70Cl 0.60K2O 0.50CaO 31.50Fe2O3 7.96Traces 0.80Sum 100.00
Phase group Phase Formula Conc.Mass %
Oxides
Maghemite+Magnetite Fe2O3+Fe3O4 2.4
Quartz SiO2 1.5
Periclase MgO 11.7
Carbonate Calcite CaCO3 36.9
Sulphates
Anhydrite CaSO4 15.7
Hydroxylellestadite Ca10(SiO4)3(SO4)3 6.7Na2SO4 Na2SO4 2.4
Glauberite Na2Ca(SO4)2 12.7
Amorphous 10
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Influence of gas atmosphere (pressure 1 bar)
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
air atmosphere
01020
3040506070
8090
100
30 200 400 600 800 1000 800 600 400 200 30
Temperature (°C)
Mas
s %
cooling
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Influence of gas atmosphere (pressure 1 bar)
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
CO2 atmosphere
01020
3040506070
8090
100
30 200 400 600 800 1000 800 600 400 200 30
Temperature (°C)
Mas
s %
air atmosphere
01020
3040506070
8090
100
30 200 400 600 800 1000 800 600 400 200 30
Temperature (°C)
Mas
s %
cooling cooling
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Influence of gas atmosphere (pressure 1 bar)
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
CO2 atmosphere
01020
3040506070
8090
100
30 200 400 600 800 1000 800 600 400 200 30
Temperature (°C)
Mas
s %
air atmosphere
01020
3040506070
8090
100
30 200 400 600 800 1000 800 600 400 200 30
Temperature (°C)
Mas
s %
cooling cooling
0
10
20
30
40
50
60
70
80
90
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C)
2 vol.% H2 in N2 atmosphere
cooling
15
Influence of pressure (air atmosphere)
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
0
10
20
30
40
50
60
70
80
90
100
30 200 400 600 800 1000 800 600 400 200 30Temperature (°C)
Mas
s %
cooling
0
10
20
30
40
50
60
70
80
90
100
30 200 400 600 800 1000 800 600 400 200 30Temperature (°C)
Mas
s %
cooling
1 bar 5 bars
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Influence of pressure (CO2 atmosphere)
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C)
5 bars
cooling
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Influence of pressure (2 vol.% hydrogen in nitrogen atmosphere)
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
0
10
20
30
40
50
60
70
80
90
100
30 200 400 600 800 1000 800 600 400 200 30Temperature (°C)
Mas
s %
cooling
0
10
20
30
40
50
60
70
80
90
100
30 200 400 600 800 1000 800 600 400 200 30Temperature (°C)
Mas
s %
cooling
1 bar 5 bars
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Thermogravimetry & Phase analyses
Sulphates (Anhydrite CaSO4, Thenardite Na2SO4, Glauberite Na2Ca (SO4)2) Carbonate (Calcite CaCO3) Ferrites (Srebrodolskite Ca2Fe2O5, CaFe2O4) Aluminate (CaAl2O4) Oxides (Quartz SiO2, Cristobalite SiO2, Periclase MgO, Lime CaO, FexOy (Magnetite, Maghemite, Hematite) Sulphide (Oldhamite CaS) Amorphous (non crystalline compounds)
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Oxides/Element
Conc.Mass %
CO2 14.28MgO 6.02Al2O3 1.89SiO2 25.59SO3 12.23Cl 0.30K2O 0.28CaO 30.20Fe2O3 8.00Traces 1.21Sum 100.00
ashing temperature - 450 °C
Si-rich lignite ash sample analyses
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Oxides/Element
Conc.Mass %
CO2 14.28MgO 6.02Al2O3 1.89SiO2 25.59SO3 12.23Cl 0.30K2O 0.28CaO 30.20Fe2O3 8.00Traces 1.21Sum 100.00
ashing temperature - 450 °C air atmosphere
Si-rich lignite ash sample analyses
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C) cooling
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Oxides/Element
Conc.Mass %
CO2 14.28MgO 6.02Al2O3 1.89SiO2 25.59SO3 12.23Cl 0.30K2O 0.28CaO 30.20Fe2O3 8.00Traces 1.21Sum 100.00
ashing temperature - 450 °C air atmosphere CO2 atmosphere
Si-rich lignite ash sample analyses
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C) cooling
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C) cooling
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Oxides/Element
Conc.Mass %
CO2 14.28MgO 6.02Al2O3 1.89SiO2 25.59SO3 12.23Cl 0.30K2O 0.28CaO 30.20Fe2O3 8.00Traces 1.21Sum 100.00
ashing temperature - 450 °C air atmosphere CO2 atmosphere
2 vol.% H2 in N2 atmosphere
Si-rich lignite ash sample analyses
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C) cooling
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C) cooling
0102030405060708090
100
30 200 400 600 800 1000 800 600 400 200 30
Mas
s %
Temperature (°C) cooling
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1 2Mass %
CO2 1.87 12.52Na2O 0.38 6.20MgO 2.99 13.91Al2O3 2.09 1.16SiO2 51.54 1.15P2O5 5.97 0.30SO3 4.55 23.70Cl 1.80 0.60K2O 16.28 0.50CaO 11.01 31.50Fe2O3 1.16 7.96Traces 0.36 0.50
1 2Phase group Phase Formula Mass %
Oxides
Quartz SiO2 7.3 1.5Maghemite+Magnetite Fe2O3+Fe3O4 - 2.4Periclase MgO - 11.7
Carbonate Calcite CaCO3 1.3 36.9Chloride Sylvite KCl 2.8 -
Sulphates
Glauberite Na2Ca(SO4)2 - 12.7Na2SO4 - 2.4Hydroxylellestadite Ca10(SiO4)3(SO4)3 - 6.7Arcanite K2SO4 8.3 -Anhydrite CaSO4 1.2 15.7
Silicate Anorthite CaAl2Si2O8 3.4 -
Phosphates
Ca10(PO4)6O 3.5 -Ca3(PO4)2 2.4 -(Ca2,589Mg0,411)(PO4)2 4.8 -
Amorphous 65 10
Comparison of biomass ash (1) & coal ash (2)
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Conclusion
Mineral composition of ash
- first phase changes take place at temperatures exceeding ashing temperature
- temperature and environment play important role
- influence of pressure show low relevance
- silicate formation at higher temperatures – slagging
- reducing atmosphere – highest mass loss