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CALCIUM EXTRACTION FROM

ESTONIAN INDUSTRIAL WASTES


BASED ON AMMONIUM SOLVENTS
Kadriann Tamm Co-authors:
Research Scientist Senior researcher Mai Uibu
Laboratory of Inorganic Materials Senior researcher Rein Kuusik
Engineer Regiina Viires
Department of Materials and Environmental Technology 1

Estonia
Outline

Background information
Methodology
Equilibrium study
Kinetic study
Results and discussion
Conclusions

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Background I
The main energy source in Estonia - oil shale - is used for
electricity and shale oil production.

The extensive use oil shale (ca 20 MT/year*) is accompanied by


vast amounts of mineral wastes - ca 7 MT/year*.

Iru waste to energy unit incinerated approximately 244 kt of


mixed municipal solid waste
(about 270 GWh of heat and 128 GWh of electricity).
Photo: AS Narva Elektrijaamad (Narva Power Plants)

Emissions of flue gases (ca 11.5 MT CO2*) is also one of the


major problems.

Currently, the wastes are deposited in the ash plateaus using


hydrotransportation.

Highly alkaline leachate waters with pH > 12 contaminate the Photo: Ash fields of the Balti Power Plants
environment and pose a risk to human health.
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* as in 2016
Background II

+ Mg 2+
Na
SiO2 K+

SO2
4 S 2 Cl
For PCC purity, it is essential to
OS ashwater suspension is able to bind up ensure the efficient but also selective
to 290 kg of CO2 per ton of ash. extraction of Ca ions.
It has been found that ammonium
The leaching of Ca ion of extent, making salts, NH4Cl, NH4NO3 and
alkaline leachates a potential source for CH3COONH4, solutions were the most
4
producing commercial by-products promising solvents for selective
(e.g. precipitated calcium carbonate PCC). extraction of calcium from steel slags
Background III

5
Fig. 1. The 2-step system of ash-solvent extraction and further carbonisation
The aims of the study

The current study focuses on Ca ion extraction from


OS and MSWI ashes using ammonium salt solvents.

The dissolution equilibrium and dynamics of the


main species was studied from the aspects of Ca ion
extraction and environmental safety.

This work examines the extraction of the Ca ion as


the first step of the complex mineral waste
utilisation process.

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Methodology I
Batch equilibrium experiments Lab Reactor for kinetic tests

Test Tube Rotator GFL 3025


Analysis of the liquid phase:
Conditions:
pH (MT SevenGo pH)
Room temperature Electrical conductivity (MT SevenGo Duo Pro)
Atmospheric pressure SO42- / S2-tot Spectrophotometrically
Air environment Cations and heavy metals - AAS (Carl Zeiss Jena
AAS IN: Verian Spectra AA 55B) 7
Characterization of the material and conditions

Oil shale ash


Ammonium CH3COOH
salt solvents
For better calcium extraction weak acid
efficiency
Circulating Circulating
Fluidized Bed ash Fluidized Bed ash
CFB1 (2011) CFB2 (2016)
NH4Cl NH4NO3 CH3COONH4
weak base - weak base - weak base and
strong acid salts strong acid salts weak acid salt
Pulverized Firing
Enefit280
cyclone ash PF

Municipal solid
waste
incinerator ash

Air Pollution 8
Control Fly ash FA
residue APC
8
System pH

0
2
4
6
8
10
12

H2O
NH4NO3
NH4Cl

APC
CH3COONH4
CH3COOH
H2O
NH4NO3
NH4Cl

FA
CH3COONH4
CH3COOH
H2O
NH4NO3
NH4Cl

pH change
CFB2
CH3COONH4
CH3COOH
H2O
NH4NO3
NH4Cl
CH3COONH4
Enefit280

final pH
CH3COOH
H2O
NH4NO3

Fig. 2. The pH of 24 h ash/solvent (1/10) system.


NH4Cl
CFB1

CH3COONH4
CH3COOH
H2O
NH4NO3
PF

NH4Cl
CH3COONH4
CH3COOH

EC , mS/cm
-50
0
50
100
150

H2O
NH4NO3
NH4Cl
APC

CH3COONH4
CH3COOH
H2O
NH4NO3
NH4Cl
FA
Results and discussion I equilibrium study

CH3COONH4
CH3COOH
H2O
NH4NO3
NH4Cl
CFB2

Conductivity change

CH3COONH4
CH3COOH
H2O
NH4NO3
NH4Cl
CH3COONH4
Enefit280

CH3COOH
H2O
NH4NO3
NH4Cl
Final conductivity
CFB1

CH3COONH4
CH3COOH
9

H2O
NH4NO3
PF

NH4Cl
CH3COONH4
CH3COOH
Fig. 3. Electrical conductivity of 24 h ash/solvent (1/10) system.
Calcium concentartion, mg/L

10000
15000
20000
25000
30000

0
5000
NH4Cl
NH4NO3
CH3COONH4

APC
CH3COOH
H2O
NH4Cl
NH4NO3
CH3COONH4

FA
CH3COOH
H2O
NH4Cl
NH4NO3
CH3COONH4
Ca2+

CFB2
CH3COOH
H2O
NH4Cl

solvent systems.
NH4NO3
Mg2+

CH3COONH4
CH3COOH
Enefit280 H2O
NH4Cl
NH4NO3
CH3COONH4
CFB1

CH3COOH
H2O
NH4Cl
NH4NO3
Fig. 4 Concentration of Ca2+ and Mg2+ ions in 24 h ash-
PF

CH3COONH4
CH3COOH
H2O
0
500
1000
1500
2000
2500
3000

Magnesim concentartion, mg/L


Sulafte cocentartion, mg/L
0
1000
2000
3000
4000
5000

NH4Cl
NH4NO3
CH3COONH4
APC

CH3COOH
H2O
NH4Cl
Results and discussion II equilibrium study

NH4NO3
CH3COONH4
FA
SO42-

extracted from this ashes using ammonium solvents.

CH3COOH
The results indicated that calcium could be selectively

H2O
NH4Cl
NH4NO3
S2-

CH3COONH4
CFB2

CH3COOH
H2O
NH4Cl
NH4NO3
CH3COONH4
CH3COOH
Enefit280

H2O
NH4Cl
NH4NO3
CH3COONH4
CFB1

CH3COOH
H2O
NH4Cl
10

NH4NO3
CH3COONH4
PF

CH3COOH
H2O
Fig. 5 Concentration of sulfur ions in 24 h ash-solvent systems.
0
2
4
8

6
10
12
14

Sulfide concentartion, mg/L


Results and discussion III - kinetic study
Vesi
H2O NH4NO3 CH3COONH4 CH3COOH
NH4CL NH4NO3 CH3COONH4 CH3COOH H2O
vesi

12 200 10

180 9
10
160 8

EC ash-solvent, mS/cm

EC ash-water, mS/cm
140 7
8
System pH

120 6

6 100 5

80 4
4
60 3

40 2
2
20 1

0 0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Time, min
Time, min
Fig. 6 Changes in system pH for ash-solvent system Fig. 7 Changes in electrical conductivity ash-solvent systems
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The changes in conductivity and pH in studied systems mainly depends on the
solvent, addition of ashes basifies the systems.
Results and discussion IV

+ () + +

+ + + + +
+ + + + + +
+

+ + + + + +
( ) + + + + + +
+

+ + + + +
( ) + + + + + +
+

+ + + +

12
Simplified dissociation for ash-solvent systems
12
Results and discussion V +
+

+
(%) =
+
The extraction efficiency of
100%
ammonium salts and acetic
acid solvents with water
90%

based systems, Ca 80%

Solvent vs water Ca extraction, %


extraction efficiency could 70%

be increased by 95%. 60%

50%
According to the main 40%
characteristics of initial 30%
ashes, using CFB2 ash gave 20%
the best results.
10%

The amount of produced 0%

NH4NO3

NH4NO3

NH4NO3

NH4NO3

NH4NO3

NH4NO3
CH3COOH
NH4Cl

NH4Cl

CH3COOH
NH4Cl

CH3COOH
NH4Cl

CH3COOH
NH4Cl

CH3COOH
NH4Cl

CH3COOH
CH3COONH4

CH3COONH4

CH3COONH4

CH3COONH4

CH3COONH4

CH3COONH4
PCC is more than 20 times
higher comparing to ash-
water system.
APC FA CFB2 Enefit280 CFB1 PF

Fig. 8 Ammonium salts and acetic acid solvents vs water Ca extraction. 13

Newest power plant at Eesti Energia is the Auvere, launched in 2015


Conclusions

For CO2 sequestration, understanding the principles of


Ca extraction is crucial.
Ca extraction from OS and MSWI ashes using
ammonium salt solvents was studied. + () + +

Ca2+ ion extraction was noticeably enhanced by + + + + +


ammonium salts solutions as compared to water + + + + + +
+

based systems + + + + + +
( ) + + + + + +

NH4NO3 solution gave the best results (extraction +

degree up to 90%). + + + + +
( ) + + + + + +
+

The proposed leaching mechanism for ash-solvent + + + +

systems can be used for future theoretical


calculations.
These results would serve as basis for the next
carbonisation step, focusing on the process
parameters that determine the quality of PCC as a
commercial product.
14
Kadriann Tamm
Tallinn University of Technology
Mobile +372 51925707
kadriann.tamm@ttu.ee
www.ttu.ee
15
ACKNOWLEDGEMENTS
The Estonian Ministry of Education and Research IUT33-19 and KIK17083 supported this study financially.
The article was published with the support of European Union via the European Regional Development Fund.