Mineral composition of ash using X-ray...

$: Mineral composition of ash using X-ray diffractometrytu-freiberg.de/sites/default/files/media/professur... · Mass % CO 2 14.28 MgO 6.02 Al 2O 3 1.89 SiO 2 25.59 SO 3 12.23 Cl 0.30$
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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




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Applications

ash/slag film

slag piece

cooling pipe corrosion

- Ash/slag investigation



Ash 1 – 815 °C Ash 1 – 1100 °C

Ash 2 – 815 °C Ash 2 – 1100 °C

Ash 3 – 815 °C Ash 3 – 1100 °C


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Mineral composition of different lignite ash samples

Ash 1 Ash 2 Ash 3

Mas

s %

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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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Na2O 6.20MgO 13.91Al2O3 1.16

SiO2 1.15


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Na2O 6.20MgO 13.91Al2O3 1.16

SiO2 1.15


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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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

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30 200 400 600 800 1000 800 600 400 200 30

Temperature (°C)

Mas

s %

cooling cooling

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CO2 atmosphere

01020

3040506070

8090

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30 200 400 600 800 1000 800 600 400 200 30

Temperature (°C)

Mas

s %

air atmosphere

01020

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8090

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30 200 400 600 800 1000 800 600 400 200 30

Temperature (°C)

Mas

s %

cooling cooling

0

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30 200 400 600 800 1000 800 600 400 200 30

Mas

s %

Temperature (°C)

2 vol.% H2 in N2 atmosphere

cooling

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Influence of pressure (air atmosphere)


0

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30 200 400 600 800 1000 800 600 400 200 30Temperature (°C)

Mas

s %

cooling

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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)


0102030405060708090

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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)


0

10

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30 200 400 600 800 1000 800 600 400 200 30Temperature (°C)

Mas

s %

cooling

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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


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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


Si-rich lignite ash sample analyses

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Oxides/Element

Conc.Mass %


ashing temperature - 450 °C air atmosphere


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 %


ashing temperature - 450 °C air atmosphere CO2 atmosphere


0102030405060708090

100

30 200 400 600 800 1000 800 600 400 200 30

Mas

s %


0102030405060708090

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30 200 400 600 800 1000 800 600 400 200 30

Mas

s %


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Oxides/Element

Conc.Mass %


ashing temperature - 450 °C air atmosphere CO2 atmosphere

2 vol.% H2 in N2 atmosphere


0102030405060708090

100

30 200 400 600 800 1000 800 600 400 200 30

Mas

s %


0102030405060708090

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30 200 400 600 800 1000 800 600 400 200 30

Mas

s %


0102030405060708090

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Mas

s %


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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

Mineral composition of ash using X-ray...

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