CO sequestration with the use of fly ash from hard coal ... · Fly ash may be the material used for CO 2 sequestration. Regardless of a low extent of absorption, as for example in

COCO22 sequestration with the use sequestration with the use of fly ash from of fly ash from

hard coal and lignite hard coal and lignite combustioncombustion

Alicja Alicja UliaszUliasz--BocheńczykBocheńczykEugeniusz MokrzyckiEugeniusz Mokrzycki

Mineral and Energy Economy Research Institute

of the Polish Academy of Sciences

2nd CO2NET EAST Workshop

CO2 Capture and Storage – Response to Climate Change

3 - 4 March 2009, Bratislava

The Polish power industry is basedThe Polish power industry is based ononconventional fuels combustionconventional fuels combustion:: hard coal and hard coal and lignitelignite.. This industry is the largest sourceThis industry is the largest source of of carbon dioxide emission in Polandcarbon dioxide emission in Poland.. Power Power generation process creates considerable quantity generation process creates considerable quantity of wastesof wastes,, including fly ash which is used in including fly ash which is used in various other industriesvarious other industries. One. One method of using fly method of using fly ash in Poland is placing it inash in Poland is placing it in aa fly ashfly ash--water water suspensions in underground coal minessuspensions in underground coal mines.. Fly ash inFly ash inaa mixture with water mightmixture with water might bebe usedused forfor carbon carbon dioxide fixation in mineral carbonation processdioxide fixation in mineral carbonation process. . POWER PLANT

CO2

FLY ASH


The The CaOCaO and free and free CaOCaO content decides largely content decides largely

about the usefulness of fly ashes in COabout the usefulness of fly ashes in CO22 bonding. bonding.

On the basis of fly ashes analysis from Polish On the basis of fly ashes analysis from Polish

professional power industry, it has been stated that professional power industry, it has been stated that

the fly ashes from lignite and the fly ashes from lignite and fluidizedfluidized bed boilers bed boilers

are characterized by the biggest are characterized by the biggest CaOCaO contents contents ((1010--

29,2%29,2%)). The lowest . The lowest CaOCaO content amounting to content amounting to

0,860,86--6,2% is present in the fly ashes from 6,2% is present in the fly ashes from

conventional hard coal combustion.conventional hard coal combustion.


Fly ashes used for COFly ashes used for CO22 fixation need to have high calcium content, fixation need to have high calcium content, which directly reacts with water. As the result of fly ash hydrawhich directly reacts with water. As the result of fly ash hydration tion the Ca(OH)the Ca(OH)22 and Cand C--HH--S phases form, which are reactive with S phases form, which are reactive with carbon dioxide. carbon dioxide.

pportlanditeortlandite

Ca(OH)Ca(OH)22 + CO+ CO22 →→ CaCOCaCO33 + H+ H22OO

calcium silicatescalcium silicates

CaOCaO··nSiOnSiO22··mHmH22O (CO (C−−SS−−H) + COH) + CO22 →→ CaCOCaCO33 + SiO+ SiO22 + mH+ mH22OO


A wide range of research has been carried out in order to A wide range of research has been carried out in order to

determine the applicability of selected fly ash from Polish determine the applicability of selected fly ash from Polish

professional power industry to COprofessional power industry to CO22 sequestration via sequestration via

mineral carbonation including:mineral carbonation including:

�� determination of COdetermination of CO22 absorption by absorption by ‘‘freshfresh’’ ashash--aqueous aqueous

suspensions suspensions

�� determination of COdetermination of CO22 bonding ratebonding rate

�� determination of COdetermination of CO22 influence on influence on leachabilityleachability of of

impurities from ashimpurities from ash--aqueous suspensionsaqueous suspensions

�� determination of COdetermination of CO22 influence on properties of ashinfluence on properties of ash--

aqueous suspensionsaqueous suspensions


Chemical composition of fly ash selected Chemical composition of fly ash selected

for for the purpose of researchthe purpose of research

5.05.06.76.77.17.11.31.3CaO CaO freefree

2.02.02.22.24.54.53.03.0MgMgOO

16.016.020.020.030.030.05.35.3CaOCaO

28.028.014.714.74.84.814.014.0AlAl22OO33

4.54.53.53.54.54.54.04.0FeFe22OO33

38.038.031.431.441.541.558.458.4SiOSiO22

FFlyly ashes from ashes from

lignite lignite

combustion in combustion in

fluidizedfluidized bed bed

boilers boilersboilers boilers


hard coal hard coal


fluidizedfluidized bed bed

boilers boilersboilers boilers


lignite lignite


conventional conventional

boilersboilers


hard coal hard coal


conventional conventional

boilersboilers

Component Component


Investigation system to determine the amount of absorbed COInvestigation system to determine the amount of absorbed CO22

cylinder CO2

Pressurechamber

Mass-flowmeter

- +

Power pack

analyzerCO2

Rectifier

Pressurechamber

Pressurechamber


Absorption of Absorption of COCO22 by ‘by ‘fresh’ ashfresh’ ash--aqueous suspensionaqueous suspension

7.527.527.037.037607601.01.0Suspension with fly ashes Suspension with fly ashes

from lignite combustion in from lignite combustion in

fluidizedfluidized bed boilers boilersbed boilers boilers


from hard coal combustion from hard coal combustion

in in fluidizedfluidized bed boilers bed boilers

boilersboilers


from lignite combustion in from lignite combustion in

conventional boilersconventional boilers


from hard coal combustion from hard coal combustion

in conventional boilersin conventional boilers

totaltotalafterafter 24 24

hourshours

COCO22 absorption absorption

[g CO[g CO22/100 g/100 g]]SSeasoning easoning

timetime

[[hh]]

AshAsh--water water

ratio ratio Suspension kindSuspension kind


Example Example chart chart of absorptionof absorption

0,0

1,0

2,0

3,0

4,0

5,0

6,0

7,0

8,0

9,0

10,0

00:00 00:14 00:28 00:43 00:57 01:12

Time [h]

Ch

am

be

r p

res

su

re [x0

,1 M

Pa

] /a

bs

orb

ed

C

O2

ma

ss

/10

0g

of a

sh

[g

]

0

5

10

15

20

25

30

35

40

45

50

Te

mp

era

ture

[o

C]

chamber pres s ure [x0,1MPa]

abs orbed CO2 mas s : gCO2/100gof as h – chamber temperature [oC]


In order to confirm COIn order to confirm CO22 bonding by ashbonding by ash--aqueous aqueous suspensions, that is the ongoing processes of mineral suspensions, that is the ongoing processes of mineral carbonation, their phase composition has been examined carbonation, their phase composition has been examined by means of by means of roentgenographicroentgenographic method, calcium carbonate method, calcium carbonate content content –– thermogravimetrythermogravimetry method and supplementary, method and supplementary, the microstructure has been examined with the use of a the microstructure has been examined with the use of a scanning microscope. In the studies the presence of calcite scanning microscope. In the studies the presence of calcite and its content has been of a particular interest, which is and its content has been of a particular interest, which is the elementary product of mineral carbonation and phases the elementary product of mineral carbonation and phases –– the products of ash hydration undergoing carbonation. the products of ash hydration undergoing carbonation. Determination of phase composition helps to state whether Determination of phase composition helps to state whether carbonation will proceed.carbonation will proceed.


0

2

4

6

8

10

12

S us pens ion withfly as hes from

hard coalcombus tion inconventional

boilers

S us pens ion withfly as hes from

lignite combus tionin conventional

boilers

Sus pens ion withfly as hes from

hard coalcombus tion influidized bed

boilers boilers

Sus pens ion withfly as hes from

lignite combus tionin fluidized bedboilers boilers

CaC

O3

cont

ent [

%]

without CO2

with CO2

CaCOCaCO33 contentcontent


Ash-aqueous suspension with the inserted CO2

Noticeable ash grains covered with microcrystalline silicates hydration, distinguishable calcite


0

0,00002

0,00004

0,00006

0,00008

0,0001

0,00012

0,00014

0,00016

0,00018

Sus pens ion with flyas hes from ha rd coa l

com bus tion inconventiona l boile rs

Sus pens ion with flya s hes from lignite

com bus tion inconventiona l boile rs


com bus tion influidized bed boile rs

Sus pens ion with flya s hes from lignite

com bus tion influidized bed boile rs

Lea

cha

bilit

y of

Pb,

mg/

dm3

without CO2

with CO2

PbPb contents in contents in leachatesleachates from ash aqueous suspensions from ash aqueous suspensions ‘‘purepure’’

and with the inserted COand with the inserted CO22


CCrr contents in contents in leachatesleachates from ash aqueous suspensions from ash aqueous suspensions ‘‘purepure’’

and with the inserted COand with the inserted CO22

0

0,001

0,002

0,003

0,004

0,005

0,006

0,007

0,008

Sus pens ion with flyas he s from ha rd coa l

combus tion inconventiona l boile rs

Sus pens ion with flyas he s from lignite

combus tion inconventiona l boile rs


combus tion influidized bed boile rs

Sus pens ion with flyas hes from lignite

combus tion influidized bed boile rs

Leac

hab

ility

of C

r, m

g/d

m3

without CO2

with CO2


Impact of COImpact of CO22 on on pH pH leachatesleachates from ash aqueous suspensionsfrom ash aqueous suspensions

0

2

4

6

8

10

12

Sus pens ion w ith flyas hes from hard coal

combus tion inconventional boilers

Sus pens ion w ith flyas hes from lignite


Sus pens ion w ith flyas hes from hard coalcombus tion in fluidized

bed boilers


combus tion in fluidizedbed boilers

pH

without CO2

with CO2


Impact of COImpact of CO22 on the compression strength of suspensionson the compression strength of suspensions

0

200

400

600

800

1000

1200

com

pres

sion

str

engt

h of

sus

pens

ions

, kP

a

Sus pens ion w ith flyas hes from hard

coal combus tion inconventional boilers



Sus pens ion w ith flyas hes from hard

coal combus tion influidized bed boilers


combus tion influidized bed boilers

without CO2

with CO2


Impact of COImpact of CO22 on the time of bonding of suspensionson the time of bonding of suspensions

0

20

40

60

80

100

120

140

160

180

Suspension with fly ashesfrom hard coal combustion in

conventional boilers

Suspension with fly ashesfrom lignite combustion in

conventional boilers

Suspension with fly ashesfrom hard coal combustion in

fluidized bed boilers

Suspension with fly ashesfrom lignite combustion in

fluidized bed boilers

time

of

bodi

ng [

h]

s ta rt time of bonding without CO2

s tart time of bonding with CO2

f inis h time of bonding without CO2

f inis h time of bonding with CO2


ConclusionsConclusions

Fly ash may be the material used for COFly ash may be the material used for CO22 sequestration. sequestration.

Regardless of a low extent of absorption, as for example in Regardless of a low extent of absorption, as for example in

suspensions based on fly ash from hard coal combustion, suspensions based on fly ash from hard coal combustion,

waste is worth considering for COwaste is worth considering for CO22 sequestration, because sequestration, because

of its great amounts. of its great amounts.

An important aspect of ashAn important aspect of ash--aqueous suspensions use for aqueous suspensions use for

COCO22 bonding is their subsequent economic usage, that will bonding is their subsequent economic usage, that will

be limited by CObe limited by CO22 influence oninfluence on leachabilityleachability of impurities of impurities

and the impact on technological properties of ‘fresh’ and and the impact on technological properties of ‘fresh’ and

hardened suspensions.hardened suspensions.



LiteratureLiterature::

1.1. UliaszUliasz--BocheBocheńńczykczyk A.,A., MokrzyckiMokrzycki E.,E., PiotrowskiPiotrowski Z., PomykaZ., Pomykałła R., 2007: a R., 2007:

The underground storage ofThe underground storage of COCO22with ashwith ash--water suspensionswater suspensions. .

EditEdit. . MEERI PAS,MEERI PAS, KrakowKrakow, , 142 p. (in Polish).142 p. (in Polish).

2. 2. UliaszUliasz--BocheBocheńńczykczyk A.,A., MokrzyckiMokrzycki E., 2006E., 2006:: Fly ashes from Fly ashes from PPolish power plants olish power plants

and combined heat and power plants and conditions of their appliand combined heat and power plants and conditions of their applicationcation

forfor carbon dioxide utilizationcarbon dioxide utilization.. Chemical Engineering Research and DesignChemical Engineering Research and Design..

VolVol.. 84, 84, IssueIssue: A9, p. 837: A9, p. 837--842842. .

3.3. UliaszUliasz--BocheBocheńńczykczyk A.,A., MokrzyckiMokrzycki E., 200E., 2008:8: COCO22 sequestration with use of fly ashsequestration with use of fly ash

from hard coal and lignite combustionfrom hard coal and lignite combustion. . Slovak Geological MagazineSlovak Geological Magazine, , specialspecial issueissue, ,

2008, p. 192008, p. 19--22.22.

4.4. WacWacłławskaawska I.I., 2007, 2007: Investigation of Bond CO: Investigation of Bond CO22 in fly ashin fly ash--water suspensions. water suspensions.

Arvieve ofArvieve of MEERI PAS,MEERI PAS, KrakowKrakow (in Polish).(in Polish).

Documents

CO sequestration with the use of fly ash from hard coal ... · Fly ash may be the material used for CO 2 sequestration. Regardless of a low extent of absorption, as for example in