The Solubility of Kraft Recovery

Boiler Precipitator Ash

Daniel Saturnino and Honghi Tran

Precipitator Ash Composition

Typical (wt%) Range (wt%)

Sodium, Na 30 28 – 35
Potassium, K 5 3 – 12
Chloride, Cl 2 0.3 – 14
Carbonate, CO3 4 0 – 15
Sulfate, SO4 59 33 – 65
Others 0.5 0.2 – 1
 Cl and K Removal Practices
• Conventional Practice
– Ash Purging
• Commercial Processes
– Leaching
– Evaporation-Crystallization
– Freeze Crystallization
– Ion Exchange
Ash Treatment Processes
 Objective
• To study the solubility of the recovery
boiler precipitator ash in water

•Determine the parameters that affect the

ash solubility and use this information to
improve the Cl and K removal
 Method
• Simulation of the system using OLI software
will be done
 Systems Studied

• Ash - water mixtures present

Na+ K+
Cl- CO32- SO42-
• Parts of the work
– pure compounds
– mixtures of compounds
– precipitator ash
 Solubility of Na2SO4 in Water
600

500
Solubility (g/kg H2O)

400 Na2SO4

300 Na2SO4*10H2O

200

100
OLI Calculation

0
0 20 40 60 80 100
Temperature (ºC)
 Solubility of Na2SO4 in Water
600

500 Na2SO4
Solubility (g/kg H2O)

400 Na2SO4*10H2O

300

200

100
OLI Calculation Literature Data
0
0 20 40 60 80 100

Temperature (ºC)
Source: Linke, W.F.; Solubilities: a compilation of data from literature; 1958
 Solubility of Na2SO4- Na2CO3 system
500
Na2CO3*H2O
400 OLI Calculation
Na2SO4 (g/kg H2O)

50ºC
300
100ºC
Burkeite
200

100
Na2SO4

0
0 100 200 300 400 500
Na2CO3 (g/kg H2O)
 Solubility of Na2SO4- Na2CO3 system
500
Na2CO3*H2O OLI Calculation
400 Solubility 100ºC
Na 2 S O 4 (g/kg H 2 O)

50ºC Solubility 50ºC

300
100ºC
Burkeite
200

100 Na2SO4

0
0 100 200 300 400 500
Na 2CO3 (g/kg H2O)

Source: Sedelnikov,I.; in Solubilities: a compilation of data from literature; 1958.

 Solubility of Systems Tested
1600
OLI Calculation (g/kg H2O)

1200 R2 = 0.98

800

400

Number of Predictions: 180

0
0 400 800 1200 1600
Literature Data (g/kg H2O)
 Solubility Test Conditions
Temperature (ºC) Concentration (g of ash/L)
Ash A 10 25 – 300
Ash C 10 25 – 400
Ash A 25 150 – 1200
Ash C 25 150 – 1000
Ash A 85 150 – 1000
Ash C 85 150 – 800
 Precipitator Ash Solubility
Ash Sample Temperature Solubility Test OLI Simulation
(ºC) (g of ash/L) (g of ash/L)

Ash A 10 116 ± 10 110

Ash C 10 142 ± 10 132
Ash A 25 418 ± 20 401
Ash C 25 403 ± 20 402
Ash A 85 419 ± 25 460
Ash C 85 400 ± 25 422
Precipitator Ash Tests
 Concentration of Ions in Liquid for
Ash A Slurry at 0.8 kg/L
60
C om position of Liquid Phase (% )

50
Na
40 K
30 Cl
CO3
20
SO4
10

0
60 70 80 90 100
Temperature (ºC)
 Concentration of Ions in Liquid for
Ash A Slurry at 85ºC
60
Composition of Liquid Phase (%)

50
Na
40
K
30 Cl
CO3
20 SO4

10

0
800 1000 1200 1400
Concentration (g of Ash per Liter)
 OLI Simulation

• OLI was used to evaluate

– Temperature
• 0 to 100ºC
– Concentration
• 0.2 to 1.4 kg/L
– Composition
• 300 different combinations
 Effect of Temperature on Liquid Composition
of Ash A - Water Mixture at 0.8 kg/L
60
Composition of Liquid Phase (%)

50 SO4

40

30 Na

20

Cl
10
K
CO3
0
0 20 40 60 80 100
Temperature (ºC)
 Effect of Concentration on Liquid
Composition of Ash A -Water Mixture at 85ºC
70

60
Composition of Liquid Phase (%)

50
SO4
40

30 Na

20 Cl

10 K
CO3
0
200 400 600 800 1000 1200 1400
Concentration (g/L)
Recycling Test
Concentration of Ions in Liquid for Recycling
Test of Ash B Slurry at 0.8 kg/L and 85ºC
60
Composition of Liquid Phase (%)

50

40 Na
K
30 Cl
CO3
20 SO4

10

0
0 1 2 3

Number of Recycles
 Conclusions

• OLI is capable of simulating the ash-water

system at wide range of conditions

• Ash solubility determined by conductimetry

is in good agreement with the simulation

• Temperature affects significantly the ash

solubility
 Conclusions
• Concentration affects the composition of
liquid phase of ash-water mixtures

• Increasing the ash concentration the

chloride content in liquid phase increases
and sulfate content decreases

• Recycling of the liquid solution from the

ash –water mixture can improve the
performance of ash treatment processes
 Future Work

• Study of the effect of sulfidity on the

mass and energy balance in the
recovery cycle

• Use WinGEMS and OLI to simulate the

recovery process
Future Work
Future Work
 Effect of Composition on the Amount of Ash
Required to Precipitate Individual Compounds

• 300 different ash compositions

• Effect of chloride and potassium content

in liquid phase
Effect of Chloride and Potassium Content on
the Amount of Ash Required to Precipitate
Na2SO4 at 100ºC
1200
Cl = mol % Cl / (Na+K)
Amount of Ash (g/kg of H 2 O)

1000

Cl = 0
800
Cl = 10
Cl = 20
600

400

200
0 5 10 15 20 25 30
mol % K/(Na+K)
Effect of Chloride and Potassium Content on
the Amount of Ash Required to Precipitate
2Na2SO4*Na2CO3 at 100ºC
1200
Cl = mol % Cl / (Na+K)
Amount of Ash (g/kg of H 2 O)

1000

800

Cl = 0
600 Cl = 10
Cl = 20
400

200
0 5 10 15 20 25 30
mol % K/(Na+K)
Effect of Chloride and Potassium Content on
the Amount of Ash Required to Precipitate
3K2SO4*Na2SO4 at 100ºC
1200
Cl = mol% Cl/(Na+K)
Amount of Ash (g/kg of H 2O)

1000

800

600

Cl = 0
400 Cl = 10
Cl = 20
200
0 5 10 15 20 25 30
mol % K/(Na+K)
 Comparison of Simulation with
Evaporation/Crystallization and
Leaching Tests of Precipitator Ash
35

30 Sodium Evap
Concentration in Reject (ppm)

Sodium Leac
25
Potassium Evap
Potassium Leac
20
Chloride Evap
Chloride Leac
15
Carbonate Evap
Carbonate Leac
10
Sulphate Evap
5 Sulphate Leac

0
800 1000 1200 1400
Concentration (g/L)
 Comparison of the results of Ions
Concentration in Liquid Phase for
Freeze Crystallization Process
300
OLI Calculation (kg/h)

200 SO4
Na

CO3
100 K

Cl

0
0 100 200 300
Literature Data (kg/h)
 Concentration of Ions in Liquid for
Recycling Test of Ash C Slurry at 0.5 kg/L
and 85ºC
60
Composition of Liquid Phase (%)

50

40 Na
K
30 Cl
CO3
20 SO4

10

0
1 2 3 4
Number of Recycling
 Amount of Ash Required to Precipitate
Individual Compounds in Ash A
1000
Na2 CO3 •10H2 O
Amount of Ash (g/kg of H2O)

KCl 3K2 SO4 •Na2SO4

800
K2 SO4
600 2Na2 SO4 •Na2CO3
Na2SO4

400 Na2SO4 •10H2O

200 Liquid solution

0
0 20 40 60 80 100
Temperature (°C)
 Amount of Ash Required to Precipitate
Individual Compounds in Ash C
1200
Amount of Ash (g/kg of H 2O)

1000 Na2 SO4

KCl
800 3K2 SO4●Na2 SO4

K2SO4
600
2Na2 SO4 ●Na2 CO3
400
Na2SO4●10H2O
200

0
0 20 40 60 80 100
Temperature ( C)
 Acknowledgements

• Pulp & Paper Centre, University of Toronto

• Members of the Research Consortium on

“Increasing Energy and Chemical Recovery
Efficiency in the Kraft Process”