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Department of Chemical & Process Engineering The high pressure interactions of coal with The high pressure interactions of coal with Implications for CO 2 disposal and CH 4 displacement from coal Mojtaba Mirzaeian Supervisor: Professor Peter.J.Hall By : By :

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Department of Chemical & Process Engineering   Field tests are expensive and a set of laboratory tests to screen coals is needed to:   Determine the irreversible storage capacity.   Measure how tightly bound CO 2 is to different coals.   Determine the physical state of CO 2 in coal. OBJECTIVES   Which coals are most effective for sequestration?

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Page 1: Department of Chemical & Process Engineering The high pressure interactions of coal with CO 2 Implications for CO 2 disposal and CH 4 displacement from

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The high pressure interactions of coal with The high pressure interactions of coal with COCO22

Implications for CO2 disposal and CH4 displacement from coal seams

Mojtaba Mirzaeian

Supervisor: Professor Peter.J.Hall

By :By :

Page 2: Department of Chemical & Process Engineering The high pressure interactions of coal with CO 2 Implications for CO 2 disposal and CH 4 displacement from

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Coal is the most abundant fossil fuel and the world depends heavily on it and will continue to do so for years to come.

There is overwhelming evidence for a gradual build up of atmospheric CO2 levels and strong evidence that this is contributing to global warming.

Unminable deep coal seams are attractive as options for the permanent sequestration of CO2

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Field tests are expensive and a set of laboratory tests to screen coals is needed to:

Determine the irreversible storage capacity. Measure how tightly bound CO2 is to different coals.Determine the physical state of CO2 in coal.

OBJECTIVESOBJECTIVES

Which coals are most effective for sequestration?

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A variety of Experimental techniques have been used :

Differential scanning calorimetry Phase change in high pressure CO2 Irreversible sorption capacity Thermodynamics

Temperature programmed desorption

Binding energy of CO2

Small angle neutron scattering

Physical state/location of CO2 in structure

ExperimentalExperimental

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-4

-3.5

-3

-2.5

-2

-1.5

-1

-0.5

0

-2

-1.5

-1

-0.5

0

40 60 80 100 120 140 160 180 200

Temperature (oC)

DSC for Wyodak coal (held in 30 bar CO2 atmospher for 24h)

second scan

first scanthird scan

endo

exoH

eat f

low

(W

/g)

Hea

t flo

w (

W/g

)

DSC results DSC results

Glass transition in coal:Glass transition in coal:

Page 6: Department of Chemical & Process Engineering The high pressure interactions of coal with CO 2 Implications for CO 2 disposal and CH 4 displacement from

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-3

-2

-1

0

1

2

3

40 60 80 100 120 140 160 180 200

Temperature (oC)

The dependence of glass transition temperature of Wyadak on the pressure of CO

2

30 bar

5 bar

10 bar

20 bar

exo

endo

Hea

t flo

w (

W/g

)

DSC resultsDSC results

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Evidence for plasticisation of Coal by CO2.

DSC resultsDSC results

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-2.5

-2

-1.5

-1

-0.5

0

0.5

1

-50 0 50 100 150 200

Temperature (oC)

DSC for Wyodak in N2 atmosphere

exo

endo

Hea

t flo

w (

W/g

)

____ First scan____ Second scan____ Third scan

-3

-2

-1

0

1

2

3

-50 0 50 100 150 200

Temperature (oC)

DSC for Wyodak in CO2 atmosphere

exo

endo

Hea

t flo

w (

W/g

)

____ First scan____ Second scan____ Third scan

DSC resultsDSC results

Irreversible strong interactions of coal with COIrreversible strong interactions of coal with CO22

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Thermodynamic of coal/COThermodynamic of coal/CO22 interactions interactions

DSC resultsDSC results

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0

1 10-11

2 10-11

3 10-11

4 10-11

5 10-11

300 350 400 450 500 550

Des

orpt

ion

rate

(arb

.un)

Temperature (K)

TPD-MS spectra of CO2 from Pittsburgh#8

Fresh sample

Sample loaded with 24 bar CO2 for 25h.

CO2 desorption from coal is an activated process.

CO2 desorption fromcoal follows a first order kinetic model.

TPD-MS resultsTPD-MS results

0

2 10-11

4 10-11

6 10-11

8 10-11

300 350 400 450 500

Des

orpt

ion

rate

(arb

.un.

)

Temperature (°K)TPD-MS spectrum of CO

2 adsorbed on

Pittsburgh#8 coal at 15 bar for 20 hours

Exp. DataRedhead Equ.

-2 10 -11

0

2 10-11

4 10-11

6 10-11

8 10-11

300 310 320 330 340 350 360

Des

orpt

ion

rate

(arb

.un.

)

Temperature (°K)

Ed= 11202 cal/mole

ß = 20 ° K /min

Kd =105378.86 S-1

Exp. Data

Redhead Equ.

Residual

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Desorption characteristics of Desorption characteristics of COCO22 from Pittsburgh #8 coal from Pittsburgh #8 coal

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0.01

0.1

1

10

100

1000

0.01 0.1 1

35 bar CO2 10 min35 bar CO2 20 min35 bar CO2 30 min35 bar CO2 1 hr35 bar CO2 1.5 hr35 bar CO2 2 hrs

Scat

terin

g cr

oss

sect

ion

(cm

-1)

Scattering wave vector q (Ao -1 )

SANS on Illinois #6 at 35 bar CO2 at various times

0.01

0.1

1

10

100

1000

0.01 0.1 1

0 bar CO225bar CO232bar CO2

Scat

terin

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oss

sect

ion

(cm

-1)

Scattering wave vector q (Ao -1 )

SANS on Illinois #6 at various CO2 pressures for 2h.

Decrease in scattering intensities after loading with CO2 gives evidence that CO2 can access to

entire pores in coal.

No change in scattering intensities with time shows that CO2 can not diffuse through the coal matrix in

the time scale of experiment.

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Coal/CO2 interactions are strong and irreversible.

Conclusions Conclusions

The values of energy of Coal/CO2 interactions decrease with increase in coal rank suggesting low rank coals are better for CO2 sequestration.

CO2 causes significant plasticisation effect in coal and changes coal structure.

CO2 desorption from coal is an activated process and follows a first order kinetic model.

Coals offer an attractive means for the long term sequestration of CO2 .

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Thank-YouThank-You

&&

QuestionsQuestions

[email protected]@strath.ac.uk

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